Polymerization process

ABSTRACT

The invention provides for polymerization catalyst compositions, and for methods for introducing the catalyst compositions into a polymerization reactor. More particularly, the method combines a catalyst component containing slurry and a catalyst component containing solution to form the completed catalyst composition for introduction into the polymerization reactor. The invention is also directed to methods of preparing the catalyst component slurry, the catalyst component solution and the catalyst compositions, to methods of controlling the properties of polymer products utilizing the catalyst compositions, and to polymers produced therefrom.

STATEMENT OF RELATED APPLICATIONS

[0001] This application is a Continuation Application claiming priorityto U.S. application Ser. No. 10/459,160 filed on Jun. 11, 2003, which isa Divisional and claims priority of U.S. application Ser. No.09/729,453, filed Dec. 4, 2000, now issued as U.S. Pat. No. 6,608,149B2.

FIELD OF THE INVENTION

[0002] The invention relates to a process for polymerizing olefin(s).Generally, the invention relates to polymerization catalystcompositions, and to methods for introducing the catalyst compositionsinto a polymerization reactor. More particularly, the method combines acatalyst component slurry with a catalyst component solution to form thecompleted catalyst composition for introduction into the polymerizationreactor. The invention also relates to methods of preparing the catalystcomponent slurries, the catalyst component solutions, and the catalystcompositions, to methods of controlling the properties of polymerproducts utilizing the catalyst compositions, and to polymers producedtherefrom.

BACKGROUND OF THE INVENTION

[0003] Advances in polymerization and catalysis have resulted in thecapability to produce many new polymers having improved physical andchemical properties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene catalyst systems and other advanced metallocene-typecatalyst systems.

[0004] To utilize these systems in industrial slurry or gas phasesprocesses, it is useful that the catalyst compound be immobilized on acarrier or support such as, for example silica or alumina. The use ofsupported or heterogeneous catalysts increases process efficiencies byassuring that the forming polymeric particles achieve a shape anddensity that improves reactor operability and ease of handling. However,bulky ligand metallocene and metallocene-type catalysts typicallyexhibit lower activity when supported than when utilized in unsupportedor homogeneous form. This “support effect” makes commercialization ofthese promising catalyst systems more difficult.

[0005] U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publicationEP-A-0 593 083 and PCT publication WO 97/46599 all describe variousprocesses and techniques for introducing liquid unsupported catalysts toa polymerization reactor.

[0006] U.S. Pat. No. 6,069,213 discloses combining a supported and anunsupported metallocene catalysts in the polymerization of olefins,European publication EP 0 965 601A disclose a combination of a solidZiegler-Natta catalyst with a liquid catalyst in toluene or Kaydolactivated with methyl alumoxane or modified methyl alumoxane, andChinese Published Patent Application No. 97116451.7 discloses combiningan unsupported metallocene with a supported methylalumoxane. None ofthese references, however, discloses a catalyst composition prepared bycontinuously combining a catalyst component slurry with a catalystcomponent solution, then introducing the combination into an operatingpolymerization reactor.

[0007] While all these methods have been described in the art, thereexists a need to reduce the support effect for bulky ligand metalloceneand metallocene-type polymerization catalyst compositions, for animproved method for introducing catalyst compositions, and especiallyfor introducing mixed catalyst compositions, into a polymerizationreactors, and for methods to control the properties of polymer productsutilizing such catalyst compositions.

SUMMARY OF THE INVENTION

[0008] The invention generally provides polymerization catalystcompositions and methods for introducing the catalyst compositions intoa polymerization reactor. More particularly, the method combines acatalyst component containing slurry and a catalyst component containingsolution to form the completed catalyst composition for introductioninto the polymerization reactor. The invention is also directed tomethods of preparing the catalyst component slurry, the catalystcomponent solution, and the catalyst compositions, to methods ofcontrolling the properties of polymer products utilizing the catalystcompositions, and to polymers produced therefrom.

[0009] In one aspect, the invention provides a process to polymerizeolefin(s) which includes the steps of continuously combining a catalystcomponent slurry with a catalyst component solution to form a catalystcomposition and introducing the catalyst composition and one or moreolefin(s) into an operating polymerization reactor.

[0010] In another aspect, the invention provides a process to controlpolymer properties which includes the steps of continuously combining acatalyst component slurry with a catalyst component solution to form acatalyst composition, introducing the catalyst composition into apolymerization reactor with one or more olefin(s) to form a polymerproduct, measuring a sample of the polymer product to obtain an initialproduct property and changing a process parameter to obtain a secondproduct property.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011]FIG. 1 illustrates an embodiment of one equipment configuration toutilize the invention.

[0012]FIG. 2 illustrates the catalyst feed configuration used forExample 2.

[0013]FIG. 3 illustrates the catalyst feed configuration used forExample 3.

[0014]FIG. 4 illustrates the catalyst feed configuration used forExample 4.

[0015]FIG. 5 is a typical SEC curve of one embodiment of the polymer.

DETAILED DESCRIPTION OF THE INVENTION

[0016] I. Introduction

[0017] The components of the catalyst composition of the inventioninclude catalyst compounds, activator compounds and support materials.The catalyst components are utilized in a slurry and/or in a solutionwhere the slurry and solution are combined then introduced into apolymerization reactor.

[0018] II. Catalyst Compounds

[0019] The catalyst compounds which may be utilized in the catalystcompositions of the invention include invention include: Group 15containing metal compounds; bulky ligand metallocene compounds;phenoxide catalyst compounds; additionally discovered catalystcompounds; and conventional-type transition metal catalysts.

[0020] A. Group 15 Containing Metal Catalyst Compound

[0021] The catalyst composition of the invention may include one or moreGroup 15 containing metal catalyst compounds. The Group 15 containingcompound generally includes a Group 3 to 14 metal atom, preferably aGroup 3 to 7, more preferably a Group 4 to 6, and even more preferably aGroup 4 metal atom, bound to at least one leaving group and also boundto at least two Group 15 atoms, at least one of which is also bound to aGroup 15 or 16 atom through another group.

[0022] In one embodiment, at least one of the Group 15 atoms is alsobound to a Group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom mayalso be bound to nothing or a hydrogen, a Group 14 atom containinggroup, a halogen, or a heteroatom containing group, and wherein each ofthe two Group 15 atoms are also bound to a cyclic group and mayoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0023] In another embodiment, the Group 15 containing metal compound ofthe present invention may be represented by the formulae:

[0024] wherein

[0025] M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, preferably a Group 4, 5, or 6 metal, and more preferably aGroup 4 metal, and most preferably zirconium, titanium or hafnium,

[0026] each X is independently a leaving group, preferably, an anionicleaving group, and more preferably hydrogen, a hydrocarbyl group, aheteroatom or a halogen, and most preferably an alkyl.

[0027] y is 0 or 1 (when y is 0 group L′ is absent),

[0028] n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

[0029] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2,

[0030] L is a Group 15 or 16 element, preferably nitrogen,

[0031] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium,

[0032] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0033] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0034] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, halogen or phosphorus, preferably a C₂ to C₂₀alkyl, aryl or aralkyl group, more preferably a linear, branched orcyclic C₂ to C₂₀ alkyl group, most preferably a C₂ to C₆ hydrocarbongroup. R¹ and R² may also be interconnected to each other.

[0035] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen

[0036] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group,

[0037] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other,

[0038] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

[0039] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, or a heteroatom containing group.

[0040] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0041] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0042] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

[0043] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0044] wherein

[0045] R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms, preferably a C₁ to C₂₀ linear or branched alkylgroup, preferably a methyl, ethyl, propyl or butyl group, any two Rgroups may form a cyclic group and/or a heterocyclic group. The cyclicgroups may be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² areindependently a methyl, ethyl, propyl or butyl group (including allisomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups,and R⁸ and R¹¹ are hydrogen.

[0046] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0047] In this embodiment, M is a Group 4 metal, preferably zirconium,titanium or hafnium, and even more preferably zirconium; each of L, Y,and Z is nitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; andR⁶ and R⁷ are absent.

[0048] In a particularly preferred embodiment the Group 15 containingmetal compound is represented by Compound 1 below:

[0049] In compound 1, Ph equals phenyl.

[0050] The Group 15 containing metal compounds utilized in the catalystcomposition of the invention are prepared by methods known in the art,such as those disclosed in EP 0 893 454 A1, U.S. Pat. No. 5,889,128 andthe references cited in U.S. Pat. No. 5,889,128 which are all hereinincorporated by reference. U.S. application Ser. No. 09/312,878, filedMay 17, 1999, discloses a gas or slurry phase polymerization processusing a supported bisamide catalyst, which is also incorporated hereinby reference.

[0051] A preferred direct synthesis of these compounds comprisesreacting the neutral ligand, (see for example YZL or YZL′ of formula Ior II) with M^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidationstate of M, each X is an anionic group, such as halide, in anon-coordinating or weakly coordinating solvent, such as ether, toluene,xylene, benzene, methylene chloride, and/or hexane or other solventhaving a boiling point above 60° C., at about 20 to about 150° C.(preferably 20 to 100° C.), preferably for 24 hours or more, thentreating the mixture with an excess (such as four or more equivalents)of an alkylating agent, such as methyl magnesium bromide in ether. Themagnesium salts are removed by filtration, and the metal complexisolated by standard techniques.

[0052] In one embodiment the Group 15 containing metal compound isprepared by a method comprising reacting a neutral ligand, (see forexample YZL or YZL′ of formula I or II) with a compound represented bythe formula M^(n)X_(n) (where M is a Group 3 to 14 metal, n is theoxidation state of M, each X is an anionic leaving group) in anon-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20 to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as toluene, xylene, benzene, and/or hexane. In anotherembodiment the solvent comprises ether and/or methylene chloride, eitherbeing preferable.

[0053] For additional information of Group 15 containing metalcompounds, please see Mitsui Chemicals, Inc. in EP 0 893 454 A1 whichdiscloses transition metal amides combined with activators to polymerizeolefins.

[0054] In one embodiment the Group 15 containing metal compound isallowed to age prior to use as a polymerization. It has been noted on atleast one occasion that one such catalyst compound (aged at least 48hours) performed better than a newly prepared catalyst compound.

[0055] B. Bulky Ligand Metallocene Compounds

[0056] The catalyst composition of the invention may include one or morebulky ligand metallocene compounds (also referred to herein asmetallocenes).

[0057] Generally, bulky ligand metallocene compounds include half andfull sandwich compounds having one or more bulky ligands bonded to atleast one metal atom. Typical bulky ligand metallocene compounds aregenerally described as containing one or more bulky ligand(s) and one ormore leaving group(s) bonded to at least one metal atom.

[0058] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably, the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0059] In one embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compoundsrepresented by the formula:

L^(A)L^(B)MQ_(n)   (III)

[0060] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafnium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of π-bonding to M. In yetanother embodiment, the atomic molecular weight (MW) of L^(A) or L^(B)exceeds 60 a.m.u., preferably greater than 65 a.m.u. In anotherembodiment, L^(A) and L^(B) may comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof Formula III only one of either L^(A) or L^(B) is present.

[0061] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Nonlimiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methy-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0062] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M. Depending on the oxidation state of the metal,the value for n is 0, 1 or 2 such that Formula III above represents aneutral bulky ligand metallocene catalyst compound.

[0063] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0064] In another embodiment, the catalyst composition of the inventionmay include one or more bulky ligand metallocene catalyst compoundswhere L^(A) and L^(B) of Formula III are bridged to each other by atleast one bridging group, A, as represented by Formula IV.

L^(A)AL^(B)MQ_(n)   (IV)

[0065] The compounds of Formula IV are known as bridged, bulky ligandmetallocene catalyst compounds. L^(A), L^(B), M, Q and n are as definedabove. Non-limiting examples of bridging group A include bridging groupscontaining at least one Group 13 to 16 atom, often referred to as adivalent moiety such as but not limited to at least one of a carbon,oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or acombination thereof. Preferably bridging group A contains a carbon,silicon or germanium atom, most preferably A contains at least onesilicon atom or at least one carbon atom. The bridging group A may alsocontain substituent groups R as defined above including halogens andiron. Non-limiting examples of bridging group A may be represented byR′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ is independently, aradical group which is hydride, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen, or halogen or twoor more R′ may be joined to form a ring or ring system. In oneembodiment, the bridged, bulky ligand metallocene catalyst compounds ofFormula IV have two or more bridging groups A (EP 664 301 B1).

[0066] In another embodiment, the bulky ligand metallocene catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(b) of Formulas III and IV are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands L^(A) and L^(B) of Formulas IIIand IV are different from each other.

[0067] Other bulky ligand metallocene catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

[0068] In another embodiment, the catalyst compositions of the inventionmay include bridged heteroatom, mono-bulky ligand metallocene compounds.These types of catalysts and catalyst systems are described in, forexample, PCT publication WO 92/00333, WO 94/07928, WO 91/04257, WO94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 andEuropean publication EP-A-0 420 436, all of which are herein fullyincorporated by reference.

[0069] In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compoundsrepresented by Formula V:

L^(C)AJMQ_(n)   (V)

[0070] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to J and L^(C); J is a heteroatomancillary ligand; and A is a bridging group; Q is a univalent anionicligand; and n is the integer 0,1 or 2. In Formula V above, L^(C), A andJ form a fused ring system. In an embodiment, L^(C) of Formula V is asdefined above for L^(A). A, M and Q of Formula V are as defined above inFormula III.

[0071] In Formula V J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

[0072] In an embodiment of the invention, the bulky ligand metallocenecatalyst compounds are heterocyclic ligand complexes where the bulkyligands, the ring(s) or ring system(s), include one or more heteroatomsor a combination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

[0073] In one embodiment, the bulky ligand metallocene catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene catalyst compounds are those described inPCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0074] In another embodiment, the bulky ligand metallocene catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which areherein fully incorporated by reference.

[0075] In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compounds isrepresented by Formula VI:

L^(D)MQ₂(YZ)X_(n)   (VI)

[0076] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; L^(D) is a bulky ligand that is bonded to M; each Q isindependently bonded to M and Q₂(YZ) forms a ligand, preferably aunicharged polydentate ligand; or Q is a univalent anionic ligand alsobonded to M; X is a univalent anionic group when n is 2 or X is adivalent anionic group when n is 1; n is 1 or 2.

[0077] In Formula VI, L and M are as defined above for Formula III. Q isas defined above for Formula III, preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0078] In another embodiment, the bulky ligand metallocene catalystcompounds are those described in PCT publications WO 99/01481 and WO98/42664, which are fully incorporated herein by reference.

[0079] Useful Group 6 bulky ligand metallocene catalyst systems aredescribed in U.S. Pat. No. 5,942,462, which is incorporated herein byreference.

[0080] Still other useful catalysts include those multinuclearmetallocene catalysts as described in WO 99/20665 and U.S. Pat. No.6,010,794, and transition metal metaaracyle structures described in EP 0969 101 A2, which are herein incorporated herein by reference. Othermetallocene catalysts include those described in EP 0 950 667 A1, doublecross-linked metallocene catalysts (EP 0 970 074 A1), tetheredmetallocenes (EP 970 963 A2) and those sulfonyl catalysts described inU.S. Pat. No. 6,008,394, which are incorporated herein by reference.

[0081] It is also contemplated that in one embodiment the bulky ligandmetallocene catalysts, described above, include their structural oroptical or enantiomeric isomers (meso and racemic isomers, for examplesee U.S. Pat. No. 5,852,143, incorporated herein by reference) andmixtures thereof.

[0082] It is further contemplated that any one of the bulky ligandmetallocene catalyst compounds, described above, have at least onefluoride or fluorine containing leaving group as described in U.S.application Ser. No. 09/191,916 filed Nov. 13, 1998.

[0083] Illustrative but non-limiting examples of bulky ligandmetallocene catalyst compounds include: bis(cyclopentadienyl)titaniumdimethyl, bis(cyclopentadienyl) titanium diphenyl,bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl) zirconiumdiphenyl, bis(cyclopentadienyl)haffium dimethyl or diphenyl,bis(cyclopentadienyl)titanium di-neopentyl,bis(cyclopentadienyl)zirconium di-neopentyl,bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)vanadium dimethyl,bis(cyclopentadienyl)titanium methyl chloride,bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclopentadienyl)zirconium methylchloride, bis(cyclopentadienyl)zirconium ethyl chloride,bis(cyclopentadienyl)zirconium phenyl chloride,bis(cyclopentadienyl)titanium methyl bromide, cyclopentadienyl titaniumtrimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienylzirconium trineopentyl, cyclopentadienyl zirconium trimethyl,cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafniumtrineopentyl, cyclopentadienyl hafnium trimethyl,pentamethylcyclopentadienyl titanium trichloride,pentaethylcyclopentadienyl titanium trichloride, bis(indenyl)titaniumdiphenyl or dichloride, bis(methylcyclopentadienyl) titanium diphenyl ordihalide, bis(1,2-dimethylcyclopentadienyl)titanium diphenyl ordichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl ordichloride, bis(pentamethyl cyclopentadienyl) titanium diphenyl ordichloride; dimethyl silyldicyclopentadienyl titanium diphenyl ordichloride, methyl phosphine dicyclopentadienyl titanium diphenyl ordichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride,isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diisobutylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride,ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconiumdichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafniium dichloride,diphenylmethylene (cyclopentadienyl)(fluorenyl)hafniium dichloride,diisopropylmethylene (cyclopentadienyl)(fluorenyl)hafium dichloride,diisobutylmethylene(cyclopentadienyl) (fluorenyl)hafnium dichloride,ditertbutylmethylene(cyclopentadienyl)(fluorenyl) hafnium dichloride,cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichbride,diisopropylmethylene(2,5-dimethylcyclopentadienyl) (fluorenyl)-hafniumdichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,diphenylmethylene (cyclopentadienyl)(fluorenyl)titanium dichloride,diisopropylmethylene (cyclopentadienyl)(fluorenyl)titanium dichloride,diisobutylmethylene (cyclopentadienyl)(fluorenyl)titanium dichloride,ditertbutylmethylene (cyclopentadienyl)(fluorenyl)titanium dichloride,cyclohexylidene(cyclopentadienyl) (fluorenyl)titanium dichloride,diisopropylmethylene(2,5 -dimethylcyclopentadienyl fluorenyl)titaniumdichloride, racemic-ethylene bis(1-indenyl)zirconium (W) dichloride,racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV)dichloride, racemic-dimethylsilyl bis (1-indenyl) zirconium (IV)dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl) zirconium (IV) dichloride,racemic-1,1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl)zirconium (IV) dichloride, ethylidene (1-indenyltetramethylcyclopentadienyl) zirconium (IV) dichloride,racemic-dimethylsilyl bis (2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium (IV) dichloride, racemic-ethylene bis (1-indenyl) hafnium (IV)dichloride, racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium(IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) hafnium (IV)dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl)hafnium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl) hafnium (IV) dichloride,racemic-1,1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl)hafnium (IV), dichloride, ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) hafnium (IV)dichloride, racemic-ethylene bis (1-indenyl) titanium (IV) dichloride,racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV)dichloride, racemic-dimethylsilyl bis (1-indenyl) titanium (IV)dichloride, racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl) titanium (IV) dichlorideracemic-1,1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1-indenyl)titanium (IV) dichloride, and ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) titanium (IV)dichloride.

[0084] Preferred bulky ligand metallocene catalyst compounds arediphenylmethylene (cyclopentadienyl)(fluorenyl)zirconium dichloride,racemic-dimethylsilyl bis (2-methyl-1-indenyl) zirconium (IV)dichloride, racemic-dimethylsilyl bis (2-methyl-4-(1-naphthyl-1-indenyl)zirconium (IV) dichloride, and racemic-dimethylsilyl bis(2-methyl-4-phenyl-1-indenyl) zirconium (IV) dichloride. Other preferredbulky ligand metallocene catalyst compounds include, indenyl zirconiumtris(diethylcarbamate), indenyl zirconium tris(pivalate), indenylzirconium tris(p-toluate), indenyl zirconium tris(benzoate),(1-methylindenyl) zirconium tris(pivalate), (2-methylindenyl) zirconiumtris(diethylcarbamate), (methylcyclopentadienyl) zirconiumtris(pivalate), cyclopentadienyl tris(pivalate), and(pentamethylcyclopentadienyl) zirconium tris(benzoate).

[0085] C. Phenoxide Catalyst Compound

[0086] The catalyst composition of the invention may include one or morephenoxide catalyst compounds represented by the following formulae:

[0087] wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably atertiary alkyl group, preferably a C₄ to C₂₀ alkyl group, preferably aC₄ to C₂₀ tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ groupand may or may not also be bound to M, and at least one of R² to R⁵ is agroup containing a heteroatom, the rest of R² to R⁵ are independentlyhydrogen or a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group(preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl,isooctyl, decyl, nonyl, dodecyl ) and any of R² to R⁵ also may or maynot be bound to M,

[0088] O is oxygen, M is a group 3 to group 10 transition metal orlanthanide metal, preferably a group 4 metal, preferably Ti, Zr or Hf, nis the valence state of the metal M, preferably 2, 3, 4, or 5, Q is analkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydrideor alkoxide group, or a bond to an R group containing a heteroatom whichmay be any of R¹ to R⁵ A heteroatom containing group may be anyheteroatom or a heteroatom bound to carbon silica or another heteroatom.Preferred heteroatoms include boron, aluminum, silicon, nitrogen,phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium.Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus,and sulfur. Even more particularly preferred heteroatoms include oxygenand nitrogen. The heteroatom itself may be directly bound to thephenoxide ring or it may be bound to another atom or atoms that arebound to the phenoxide ring. The heteroatom containing group may containone or more of the same or different heteroatoms. Preferred heteroatomgroups include imines, amines, oxides, phosphines, ethers, ketenes,oxoazolines heterocyclics, oxazolines, thioethers, and the like.Particularly preferred heteroatom groups include imines. Any twoadjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

[0089] In a preferred embodiment, Q is a bond to any of R² to R⁵ and theR group that Q is bound to is a heteroatom containing group.

[0090] This invention may also be practiced with the catalysts disclosedin EP 0 874 005 A1, which in incorporated by reference herein.

[0091] In a preferred embodiment the phenoxide catalyst compoundcomprises one or more of:

[0092] bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0093] bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0094] bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

[0095] bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0096] bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0097] bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0098] bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0099] bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0100] bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dichloride;

[0101] bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dipivalate;

[0102] bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV) dipivalate;

[0103] bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

[0104] bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

[0105] bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;

[0106]bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

[0107]bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

[0108]bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

[0109]bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

[0110]bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

[0111]bis(N-hexyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

[0112]bis(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

[0113]bis(N-iso-propyl-3,5-di-(1′-methylcyclohexyl)lsalicylimino)zirconium(IV)dibenzyl;

[0114] bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV) dibenzyl;

[0115] bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

[0116] bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

[0117] bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV) dibenzyl;

[0118]bis(N-benzyl-3-(2′,6′-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

[0119] bis(N-benzyl-3-(2′,6′-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

[0120] bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

[0121] bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

[0122] bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

[0123] bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)

[0124] di(bis(dimethylamide));bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

[0125] bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

[0126]bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

[0127]bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

[0128]bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

[0129] (N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

[0130](N-(2′,6′-di-iso-propylphenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

[0131](N-(2′,6′-di-iso-propylphenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and(N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV) trichloride.

[0132] D. Additional Catalyst Compounds

[0133] The catalyst compositions of the invention may include one ormore complexes known as transition metal catalysts based on bidentateligands containing pyridine or quinoline moieties, such as thosedescribed in U.S. application Ser. No. 09/103,620 filed Jun. 23, 1998,which is herein incorporated by reference.

[0134] In one embodiment, these catalyst compounds are represented bythe formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)   (IX)

[0135] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0136] It is within the scope of this invention, in one embodiment, thecatalyst compounds include complexes of Ni²⁺ and Pd²⁺ described in thearticles Johnson, et al., “New Pd(II)- and Ni(II)-Based Catalysts forPolymerization of Ethylene and a-Olefins”, J. Am. Chem. Soc. 1995, 117,6414-6415 and Johnson, et al., “Copolymerization of Ethylene andPropylene with Functionalized Vinyl Monomers by Palladium(II)Catalysts”, J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010published Aug. 1, 1996, WO 99/02472, U.S. Pat. Nos. 5,852,145, 5,866,663and 5,880,241, which are all herein fully incorporated by reference.These complexes can be either dialkyl ether adducts, or alkylatedreaction products of the described dihalide complexes that can beactivated to a cationic state by the activators of this inventiondescribed below.

[0137] Other catalyst compounds include those nickel complexes describedin WO 99/50313, which is incorporated herein by reference.

[0138] Also included are those diimine based ligands of Group 8 to 10metal catalyst compounds disclosed in PCT publications WO 96/23010 andWO 97/48735 and Gibson, et al., Chem. Comm., pp. 849-850 (1998), all ofwhich are herein incorporated by reference.

[0139] Other useful catalyst compounds are those Group 5 and 6 metalimido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition,metallocene catalysts include bridged bis(arylamido) Group 4 compoundsdescribed by D. H. McConville, et al., in Organometallics 1195, 14,5478-5480, which is herein incorporated by reference. In addition,bridged bis(amido) catalyst compounds are described in WO 96/27439,which is herein incorporated by reference. Other useful catalysts aredescribed as bis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No.5,852,146, which is incorporated herein by reference. Other usefulcatalysts containing one or more Group 15 atoms include those describedin WO 98/46651, which is herein incorporated herein by reference.

[0140] E. Conventional Transition Metal Catalysts

[0141] In another embodiment, conventional-type transition metalcatalysts may be used in the practice of this invention.Conventional-type transition metal catalysts are those traditionalZiegler-Natta, vanadium and Phillips-type catalysts well known in theart. Such as, for example Ziegler-Natta catalysts as described inZiegler-Natta Catalysts and Polymerizations, John Boor, Academic Press,New York, 1979. Examples of conventional-type transition metal catalystsare also discussed in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687,4,564,605, 4,721,763, 4,879,359 and 4,960,741, all of which are hereinfully incorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 17, preferably 4 to 12, morepreferably 4 to 6 of the Periodic Table of Elements.

[0142] Preferred conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups 3 to17, preferably Group 4 to 6, more preferably Group 4, most preferablytitanium; R is a halogen or a hydrocarbyloxy group; and x is theoxidation state of the metal M. Non-limiting examples of R includealkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examplesof conventional-type transition metal catalysts where M is titaniuminclude TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃.⅓AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

[0143] Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

[0144] British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036,herein incorporated by reference, describes various conventional-typevanadium catalyst compounds. Non-limiting examples of conventional-typevanadium catalyst compounds include vanadyl trihalide, alkoxy halidesand alkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

[0145] Conventional-type chromium catalyst compounds, often referred toas Phillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

[0146] Still other conventional-type transition metal catalyst compoundsand catalyst systems suitable for use in the present invention aredisclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062,4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and5,869,585 and published EP-A2 0 416 815 A2 and EP-A1 0 420 436, whichare all herein incorporated by reference.

[0147] Other catalysts may include cationic catalysts such as AlCl₃, andother cobalt, iron, nickel and palladium catalysts well known in theart. See for example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and4,689,437, all of which are incorporated herein by reference.

[0148] It is also contemplated that other catalysts can be combined withthe catalyst compounds in the catalyst composition of the invention. Forexample, see U.S. Pat. Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015,5,470,811, and 5,719,241 all of which are herein fully incorporatedherein reference.

[0149] It is further contemplated that one or more of the catalystcompounds described above or catalyst systems may be used in combinationwith one or more conventional catalyst compounds or catalyst systems.Non-limiting examples of mixed catalysts and catalyst systems aredescribed in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418,5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and5,767,031 and PCT Publication WO 96/23010 published Aug. 1, 1996, all ofwhich are herein fully incorporated by reference.

[0150] III. Activators and Activation Methods for Catalyst Compounds

[0151] The polymerization catalyst compounds, described above, aretypically activated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts.

[0152] A. Aluminoxane and Aluminum Alkyl Activators

[0153] In one embodiment, alumoxanes activators are utilized as anactivator in the catalyst composition of the invention. Alumoxanes aregenerally oligomeric compounds containing —Al(R)—O— subunits, where R isan alkyl group. Examples of alumoxanes include methylalumoxane (MAO),modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.Alumoxanes may be produced by the hydrolysis of the respectivetrialkylaluminum compound. MMAO may be produced by the hydrolysis oftrimethylalumium and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in U.S. Pat. No. 4,665,208, 4,952,540, 5,091,352,5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031,5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656,5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publicationsEP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, andPCT publications WO 94/10180 and WO 99/15534, all of which are hereinfully incorporated by reference. A another alumoxane is a modifiedmethyl alumoxane (MMAO) cocatalyst type 3A (commercially available fromAkzo Chemicals, Inc. under the trade name Modified Methylalumoxane type3A, covered under patent number U.S. Pat. No. 5,041,584).

[0154] Aluminum Alkyl or organoaluminum compounds which may be utilizedas activators include trimethylalumium, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

[0155] B. Ionizing Activators

[0156] It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

[0157] Examples of neutral stoichiometric activators includetri-substituted boron, tellurium, aluminum, gallium and indium ormixtures thereof. The three substituent groups are each independentlyselected from alkyls, alkenyls, halogen, substituted alkyls, aryls,arylhalides, alkoxy and halides. Preferably, the three groups areindependently selected from halogen, mono or multicyclic (includinghalosubstituted) aryls, alkyls, and alkenyl compounds and mixturesthereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkylgroups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbonatoms and aryl groups having 3 to 20 carbon atoms (including substitutedaryls). More preferably, the three groups are alkyls having 1 to 4carbon groups, phenyl, napthyl or mixtures thereof. Even morepreferably, the three groups are halogenated, preferably fluorinated,aryl groups. Most preferably, the neutral stoichiometric activator istrisperfluorophenyl boron or trisperfluoronapthyl boron.

[0158] Ionic stoichiometric activator compounds may contain an activeproton, or some other cation associated with, but not coordinated to, oronly loosely coordinated to, the remaining ion of the ionizing compound.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0159] In a preferred embodiment, the stoichiometric activators includea cation and an anion component, and may be represented by the followingformula:

(L-H)_(d) ⁺(A^(d−))   (X)

[0160] wherein L is an neutral Lewis base;

[0161] H is hydrogen;

[0162] (L-H)⁺ is a Bronsted acid

[0163] A^(d−) is a non-coordinating anion having the charge d−

[0164] is an integer from 1 to 3.

[0165] The cation component, (L-H)_(d) ⁺ may include Bronsted acids suchas protons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene or Group 15 containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

[0166] The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capableof donating a proton to the transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. The activating cation (L-H)_(d) ⁺ may also be anabstracting moiety such as silver, carboniums, tropylium, carbeniums,ferroceniums and mixtures, preferably carboniums and ferroceniums. Mostpreferably (L-H)_(d) ⁺ is triphenyl carbonium.

[0167] The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

[0168] Illustrative, but not limiting examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are tri-substituted ammonium saltssuch as:

[0169] trimethylammonium tetraphenylborate,

[0170] triethylammonium tetraphenylborate,

[0171] tripropylammonium tetraphenylborate,

[0172] tri(n-butyl)ammonium tetraphenylborate,

[0173] tri(t-butyl)ammonium tetraphenylborate,

[0174] N,N-dimethylanilinium tetraphenylborate,

[0175] N,N-diethylanilinium tetraphenylborate,

[0176] N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,

[0177] trimethylammonium tetrakis(pentafluorophenyl)borate,

[0178] triethylammonium tetrakis(pentafluorophenyl)borate,

[0179] tripropylammonium tetrakis(pentafluorophenyl)borate,

[0180] tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0181] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[0182] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0183] N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

[0184] N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl) borate,

[0185] trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

[0186] triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,

[0187] tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,

[0188] tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

[0189] dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0190] N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

[0191] N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

[0192]N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

[0193] dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl) borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl) borate; and tri-substituted phosphoniumsalts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate.

[0194] Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺(A^(d−)) is N,N-dimethylanilinium tetra(perfluorophenyl)borate ortriphenylcarbenium tetra(perfluorophenyl)borate.

[0195] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing abulky ligand metallocene catalyst cation and their non-coordinatinganion are also contemplated, and are described in EP-A-0 426 637, EP-A-0573 403 and U.S. Pat. No. 5,387,568, which are all herein incorporatedby reference.

[0196] C. Conventional-Type Cocatalysts

[0197] Typically, conventional transition metal catalyst compoundsexcluding some conventional-type chromium catalyst compounds areactivated with one or more of the conventional cocatalysts which may berepresented by the formula M³M⁴ _(v)X² _(c)R³ _(b−c), wherein M³ is ametal from Group 1 to 3 and 12 to 13 of the Periodic Table of Elements;M⁴ is a metal of Group 1 of the Periodic Table of Elements; v is anumber from 0 to 1; each X² is any halogen; c is a number from 0 to 3;each R³ is a monovalent hydrocarbon radical or hydrogen; b is a numberfrom 1 to 4; and wherein b minus c is at least 1. Otherconventional-type organometallic cocatalyst compounds for the aboveconventional-type transition metal catalysts have the formula M³R³ _(k),where M³ is a Group IA, IIA, IIB or IIIA metal, such as lithium, sodium,beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals1, 2 or 3 depending upon the valency of M³ which valency in turnnormally depends upon the particular Group to which M³ belongs; and eachR³ may be any monovalent hydrocarbon radical.

[0198] Non-limiting examples of conventional-type organometalliccocatalyst compounds useful with the conventional-type catalystcompounds described above include methyllithium, butyllithium,dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium,diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylalumium,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude monoorganohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide, diisobutylaluminum hydride, methylcadmium hydride, diethylboron hydride,hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride,butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride andbromocadmium hydride. Conventional-type organometallic cocatalystcompounds are known to those in the art and a more complete discussionof these compounds may be found in U.S. Pat. Nos. 3,221,002 and5,093,415, which are herein fully incorporated by reference.

[0199] D. Additional Activators

[0200] Other activators include those described in PCT publication WO98/07515 such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

[0201] Other suitable activators are disclosed in WO 98/09996,incorporated herein by reference, which describes activating bulkyligand metallocene catalyst compounds with perchlorates, periodates andiodates including their hydrates. WO 98/30602 and WO 98/30603,incorporated by reference, describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for a bulkyligand metallocene catalyst compound. WO 99/18135, incorporated hereinby reference, describes the use of organoboron-aluminum acitivators.EP-B1-0 781 299 describes using a silylium salt in combination with anon-coordinating compatible anion. Also, methods of activation such asusing radiation (see EP-B1-0 615 981 herein incorporated by reference),electrochemical oxidation, and the like are also contemplated asactivating methods for the purposes of rendering the neutral bulkyligand metallocene catalyst compound or precursor to a bulky ligandmetallocene cation capable of polymerizing olefins. Other activators ormethods for activating a bulky ligand metallocene catalyst compound aredescribed in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

[0202] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula: (OX^(e+))_(d)(A^(d−))_(e) wherein:OX^(e+) is a cationic oxidizing agent having a charge of e+; e is aninteger from 1 to 3; and A⁻, and d are as previously defined. Examplesof cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

[0203] It within the scope of this invention that catalyst compounds canbe combined one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157 and 5,453,410, European publication EP-B1 0 573120, and PCT publications WO 94/07928 and WO 95/14044. These documentsall discuss the use of an alumoxane and an ionizing activator with abulky ligand metallocene catalyst compound.

[0204] IV. Supports, Carriers and General Supporting Techniques

[0205] The catalyst composition of the invention includes a supportmaterial or carrier, and preferably includes a supported activator. Forexample, the catalyst composition component, preferably the activatorcompound and/or the catalyst compound, is deposited on, contacted with,vaporized with, bonded to, or incorporated within, adsorbed or absorbedin, or on, a support or carrier.

[0206] A. Support Material

[0207] The support material is any of the conventional supportmaterials. Preferably the supported material is a porous supportmaterial, for example, talc, inorganic oxides and inorganic chlorides.Other support materials include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, or any other organic or inorganic support material andthe like, or mixtures thereof.

[0208] The preferred support materials are inorganic oxides that includethose Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supportsinclude silica, fumed silica, alumina (WO 99/60033), silica-alumina andmixtures thereof. Other useful supports include magnesia, titania,zirconia, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite(European Pat. EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays(U.S. Pat. No. 6,034,187) and the like. Also, combinations of thesesupport materials may be used, for example, silica-chromium,silica-alumina, silica-titania and the like. Additional supportmaterials may include those porous acrylic polymers described in EP 0767 184 B1, which is incorporated herein by reference. Other supportmaterials include nanocomposites as described in PCT WO 99/47598,aerogels as described in WO 99/48605, spherulites as described in U.S.Pat. No. 5,972,510 and polymeric beads as described in WO 99/50311,which are all herein incorporated by reference. A preferred support isfumed silica available under the trade name Cabosil™ TS-610, availablefrom Cabot Corporation. Fumed silica is typically a silica withparticles 7 to 30 nanometers in size that has been treated withdimethylsilyldichloride such that a majority of the surface hydroxylgroups are capped.

[0209] It is preferred that the support material, most preferably aninorganic oxide, has a surface area in the range of from about 10 toabout 700 m²/g, pore volume in the range of from about 0.1 to about 4.0cc/g and average particle size in the range of from about 5 to about 500μm. More preferably, the surface area of the support material is in therange of from about 50 to about 500 m²/g, pore volume of from about 0.5to about 3.5 cc/g and average particle size of from about 10 to about200 μm. Most preferably the surface area of the support material is inthe range is from about 100 to about 400 m²/g, pore volume from about0.8 to about 3.0 cc/g and average particle size, is from about 5 toabout 100 μm. The average pore size of the carrier of the inventiontypically has pore size in the range of from 10 to 1000 Å, preferably 50to about 500 Å, and most preferably 75 to about 350 Å.

[0210] The support materials may be treated chemically, for example witha fluoride compound as described in WO 00/12565, which is hereinincorporated by reference. Other supported activators are described infor example WO 00/13792 that refers to supported boron containing solidacid complex.

[0211] In a preferred method of forming a supported catalyst compositioncomponent, the amount of liquid in which the activator is present is inan amount that is less than four times the pore volume of the supportmaterial, more preferably less than three times, even more preferablyless than two times; preferred ranges being from 1.1 times to 3.5 timesrange and most preferably in the 1.2 to 3 times range. In an alternativeembodiment, the amount of liquid in which the activator is present isfrom one to less than one times the pore volume of the support materialutilized in forming the supported activator.

[0212] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0213] B. Supported Activators

[0214] In one embodiment, the catalyst composition includes a supportedactivator. Many supported activators are described in various patentsand publications which include: U.S. Pat. No. 5,728,855 directed to theforming a supported oligomeric alkylaluminoxane formed by treating atrialkylaluminum with carbon dioxide prior to hydrolysis; U.S. Pat. Nos.5,831,109 and 5,777,143 discusses a supported methylalumoxane made usinga non-hydrolytic process; U.S. Pat. No. 5,731,451 relates to a processfor making a supported alumoxane by oxygenation with a trialkylsiloxymoiety; U.S. Pat. No. 5,856,255 discusses forming a supported auxiliarycatalyst (alumoxane or organoboron compound) at elevated temperaturesand pressures; U.S. Pat. No. 5,739,368 discusses a process of heattreating alumoxane and placing it on a support; EP-A-0 545 152 relatesto adding a metallocene to a supported alumoxane and adding moremethylalumoxane; U.S. Pat. Nos. 5,756,416 and 6,028,151 discuss acatalyst composition of a alumoxane impregnated support and ametallocene and a bulky aluminum alkyl and methylalumoxane; EP-B1-0 662979 discusses the use of a metallocene with a catalyst support of silicareacted with alumoxane; PCT WO 96/16092 relates to a heated supporttreated with alumoxane and washing to remove unfixed alumoxane; U.S.Pat. Nos. 4,912,075, 4,937,301, 5,008,228, 5,086,025, 5,147,949,4,871,705, 5,229,478, 4,935,397, 4,937,217 and 5,057,475, and PCT WO94/26793 all directed to adding a metallocene to a supported activator;U.S. Pat. No. 5,902,766 relates to a supported activator having aspecified distribution of alumoxane on the silica particles; U.S. Pat.No. 5,468,702 relates to aging a supported activator and adding ametallocene; U.S. Pat. No. 5,968,864 discusses treating a solid withalumoxane and introducing a metallocene; EP 0 747 430 A1 relates to aprocess using a metallocene on a supported methylalumoxane andtrimethylalumium; EP 0 969 019 A1 discusses the use of a metallocene anda supported activator; EP-B2-0 170 059 relates to a polymerizationprocess using a metallocene and a organo-aluminuim compound, which isformed by reacting aluminum trialkyl with a water containing support;U.S. Pat. No. 5,212,232 discusses the use of a supported alumoxane and ametallocene for producing styrene based polymers; U.S. Pat. No.5,026,797 discusses a polymerization process using a solid component ofa zirconium compound and a water-insoluble porous inorganic oxidepreliminarily treated with alumoxane; U.S. Pat. No. 5,910,463 relates toa process for preparing a catalyst support by combining a dehydratedsupport material, an alumoxane and a polyfunctional organic crosslinker;U.S. Pat. Nos. 5,332,706, 5,473,028, 5,602,067 and 5,420,220 discusses aprocess for making a supported activator where the volume of alumoxanesolution is less than the pore volume of the support material; WO98/02246 discusses silica treated with a solution containing a source ofaluminum and a metallocene; WO 99/03580 relates to the use of asupported alumoxane and a metallocene; EP-A1-0 953 581 discloses aheterogeneous catalytic system of a supported alumoxane and ametallocene; U.S. Pat. No. 5,015,749 discusses a process for preparing apolyhydrocarbyl-alumoxane using a porous organic or inorganic imbibermaterial; U.S. Pat. Nos. 5,446,001 and 5,534,474 relates to a processfor preparing one or more alkylaluminoxanes immobilized on a solid,particulate inert support; and EP-A1-0 819 706 relates to a process forpreparing a solid silica treated with alumoxane. Also, the followingarticles, also fully incorporated herein by reference for purposes ofdisclosing useful supported activators and methods for theirpreparation, include: W. Kaminsky, et al., “Polymerization of Styrenewith Supported Half-Sandwich Complexes”, Journal of Polymer Science Vol.37, 2959-2968 (1999) describes a process of adsorbing a methylalumoxaneto a support followed by the adsorption of a metallocene; Junting Xu, etal. “Characterization of isotactic polypropylene prepared withdimethylsilyl bis(1indenyl)zirconium dichloride supported onmethylaluminoxane pretreated silica”, European Polymer Journal 35 (1999)1289-1294, discusses the use of silica treated with methylalumoxane anda metallocene; Stephen O'Brien, et al., “EXAFS analysis of a chiralalkene polymerization catalyst incorporated in the mesoporous silicateMCM-41” Chem. Commun. 1905-1906 (1997) discloses an immobilizedalumoxane on a modified mesoporous silica; and F. Bonini, et al.,“Propylene Polymerization through Supported Metallocene/MAO Catalysts:Kinetic Analysis and Modeling” Journal of Polymer Science, Vol. 332393-2402 (1995) discusses using a methylalumoxane supported silica witha metallocene. Any of the methods discussed in these references areuseful for producing the supported activator component utilized in thecatalyst composition of the invention and all are incorporated herein byreference.

[0215] In another embodiment, the supported activator, such as supportedalumoxane, is aged for a period of time prior to use herein. Forreference please refer to U.S. Pat. Nos. 5,468,702 and 5,602,217,incorporated herein by reference.

[0216] In an embodiment, the supported activator is in a dried state ora solid. In another embodiment, the supported activator is in asubstantially dry state or a slurry, preferably in a mineral oil slurry.

[0217] In another embodiment, two or more separately supportedactivators are used, or alternatively, two or more different activatorson a single support are used.

[0218] In another embodiment, the support material, preferably partiallyor totally dehydrated support material, preferably 200° C. to 600° C.dehydrated silica, is then contacted with an organoaluminum or alumoxanecompound. Preferably in an embodiment where an organoaluminum compoundis used, the activator is formed in situ on and in the support materialas a result of the reaction of, for example, trimethylalumium and water.

[0219] In another embodiment, Lewis base-containing supports are reactedwith a Lewis acidic activator to form a support bonded Lewis acidcompound. The Lewis base hydroxyl groups of silica are exemplary ofmetal/metalloid oxides where this method of bonding to a support occurs.This embodiment is described in U.S. patent application Ser. No.09/191,922, filed Nov. 13, 1998, which is herein incorporated byreference.

[0220] Other embodiments of supporting an activator are described inU.S. Pat. No. 5,427,991, where supported non-coordinating anions derivedfrom trisperfluorophenyl boron are described; U.S. Pat. No. 5,643,847discusses the reaction of Group 13 Lewis acid compounds with metaloxides such as silica and illustrates the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions; immobilized Group IIIALewis acid catalysts suitable for carbocationic polymerizations aredescribed in U.S. Pat. No. 5,288,677; and James C. W. Chien, Jour. Poly.Sci.: Pt A: Poly. Chem, Vol. 29, 1603-1607 (1991), describes the olefinpolymerization utility of methylalumoxane (MAO) reacted with silica(SiO₂) and metallocenes and describes a covalent bonding of the aluminumatom to the silica through an oxygen atom in the surface hydroxyl groupsof the silica.

[0221] In a preferred embodiment, a supported activator is formed bypreparing in an agitated, and temperature and pressure controlled vessela solution of the activator and a suitable solvent, then adding thesupport material at temperatures from 0° C. to 100° C., contacting thesupport with the activator solution for up to 24 hours, then using acombination of heat and pressure to remove the solvent to produce a freeflowing powder. Temperatures can range from 40 to 120° C. and pressuresfrom 5 psia to 20 psia (34.5 to 138 kPa). An inert gas sweep can also beused in assist in removing solvent. Alternate orders of addition, suchas slurrying the support material in an appropriate solvent then addingthe activator, can be used.

[0222] C. Spray Dried Catalyst Composition Components

[0223] In another embodiment a support is combined with one or moreactivators and is spray dried to form a supported activator. In apreferred embodiment, fumed silica is combined with methyl alumoxane andthen spray dried to from supported methyl alumoxane. Preferably asupport is combined with alumoxane, spray dried and then placed inmineral oil to form a slurry useful in the instant invention.

[0224] In another embodiment, the catalyst compounds described abovehave been combined with optional support material(s) and or optionalactivator(s) and spray dried prior to being combined with the slurrydiluent.

[0225] In another embodiment, the catalyst compounds and/or theactivators are preferably combined with a support material such as aparticulate filler material and then spray dried, preferably to form afree flowing powder. Spray drying may be by any means known in the art.Please see EP A 0 668 295 B1, U.S. Pat. No. 5,674,795 and U.S. Pat. No.5,672,669 and U.S. patent application Ser. No. 09/464,114 filed Dec. 16,1999, which particularly describe spray drying of supported catalysts.In general one may spray dry the catalysts by placing the catalystcompound and the optional activator in solution (allowing the catalystcompound and activator to react, if desired), adding a filler materialsuch as silica or fumed silica, such as Gasil™ or Cabosil™, then forcingthe solution at high pressures through a nozzle. The solution may besprayed onto a surface or sprayed such that the droplets dry in midair.The method generally employed is to disperse the silica in toluene, stirin the activator solution, and then stir in the catalyst compoundsolution. Typical slurry concentrations are about 5 to 8 wt %. Thisformulation may sit as a slurry for as long as 30 minutes with mildstirring or manual shaking to keep it as a suspension beforespray-drying. In one preferred embodiment, the makeup of the driedmaterial is about 40-50 wt % activator (preferably alumoxane), 50-60SiO₂ and about ˜2 wt % catalyst compound.

[0226] For simple catalyst compound mixtures, the two or more catalystcompounds can be added together in the desired ratio in the last step.In another embodiment, more complex procedures are possible, such asaddition of a first catalyst compound to the activator/filler mixturefor a specified reaction time t, followed by the addition of the secondcatalyst compound solution, mixed for another specified time x, afterwhich the mixture is cosprayed. Lastly, another additive, such as1-hexene in about 10 vol % can be present in the activator/fillermixture prior to the addition of the first metal catalyst compound.

[0227] In another embodiment binders are added to the mix. These can beadded as a means of improving the particle morphology, i.e. narrowingthe particle size distribution, lower porosity of the particles andallowing for a reduced quantity of alumoxane, which is acting as the‘binder’.

[0228] In another embodiment a solution of a bulky ligand metallocenecompound and optional activator can be combined with a differentslurried spray dried catalyst compound and then introduced into areactor.

[0229] The spray dried particles are generally fed into thepolymerization reactor as a mineral oil slurry. Solids concentrations inoil are about 10 to 30 weight %, preferably 15 to 25 weight %. In someembodiments, the spray dried particles can be from less than about 10micrometers in size up to about 100 micrometers, compared toconventional supported catalysts which are about 50 micrometers. In apreferred embodiment the support has an average particle size of 1 to 50microns, preferably 10 to 40 microns.

[0230] V. Catalyst Compositions of the Invention

[0231] To prepare the catalyst composition of the invention, thecatalyst components described above are utilized in a catalyst componentslurry and/or in a catalyst component solution. For the purposes of thisinvention, a slurry is defined to be a suspension of a solid, where thesolid may or may not be porous, in a liquid. The catalyst componentslurry and the catalyst component solution are combined to form thecatalyst composition which is then introduced into a polymerizationreactor.

[0232] A. Catalyst Component Slurry

[0233] In one embodiment, the catalyst component slurry includes anactivator and a support, or a supported activator. In anotherembodiment, the slurry also includes a catalyst compound in addition tothe activator and the support and/or the supported activator. In oneembodiment, the catalyst compound in the slurry is supported.

[0234] In another embodiment, the slurry includes one or moreactivator(s) and support(s) and/or supported activator(s) and/or onemore catalyst compound(s). For example, the slurry may include two ormore activators (such as a supported alumoxane and a modified alumoxane)and a catalyst compound, or the slurry may include a supported activatorand more than one catalyst compounds. Preferably, the slurry comprises asupported activator and two catalyst compounds.

[0235] In another embodiment the slurry comprises supported activatorand two different catalyst compounds, which may be added to the slurryseparately or in combination.

[0236] In another embodiment the slurry, containing a supportedalumoxane, is contacted with a catalyst compound, allowed to react, andthereafter the slurry is contacted with another catalyst compound. Inanother embodiment the slurry containing a supported alumoxane iscontacted with two catalyst compounds at the same time, and allowed toreact.

[0237] In another embodiment the molar ratio of metal in the activatorto metal in the catalyst compound in the slurry is 1000:1 to 0.5:1,preferably 300:1 to 1:1, more preferably 150:1 to 1:1.

[0238] In another embodiment the slurry contains a support materialwhich may be any inert particulate carrier material known in the art,including, but not limited to, silica, fumed silica, alumina, clay, talcor other support materials such as disclosed above. In a preferredembodiment, the slurry contains a supported activator, such as thosedisclosed above, preferably methyl alumoxane and/or modified methylalumoxane on a support of silica.

[0239] The catalyst component slurry used in the process of thisinvention is typically prepared by suspending the catalyst components,preferably the support, the activator and optional catalyst compounds ina liquid diluent. The liquid diluent is typically an alkane having from3 to 60 carbon atoms, preferably having from 5 to 20 carbon atoms,preferably a branched alkane, or an organic composition such as mineraloil or silicone oil. The diluent employed is preferably liquid under theconditions of polymerization and relatively inert. The concentration ofthe components in the slurry is controlled such that a desired ratio ofcatalyst compound(s) to activator, and/or catalyst compound to catalystcompound is fed into the reactor.

[0240] Typically, the catalyst compound and the support and activator,or supported activator, and the slurry diluent are allowed to contacteach other for a time sufficient for at least 50% of the catalystcompounds to be deposited into or on the support, preferably at least70%, preferably at least 75%, preferably at least 80%, more preferablyat least 90%, preferably at least 95%, preferably at least 99%. In anembodiment, the catalyst component slurry is prepared prior to its usein the catalyst feed system of the invention. Times allowed for mixingare up to 10 hours, typically up to 6 hours, more typically 4 to 6hours. In one embodiment of this invention a catalyst compound will beconsidered to be in or on the support if the concentration of thecatalyst compound in the liquid portion of the slurry is reduced overtime after adding the catalyst compound to the slurry. Concentration ofthe catalyst compound in the liquid diluent may be measured for example,by inductively coupled plasma spectroscopy (ICPS), or by ultraviolet(UV) spectroscopy, after standardization with a calibration curveprepared at the appropriate concentration range, as is known in the art.Thus for example, 70% of a catalyst compound will be considered to havedeposited in or on a support if the concentration of the catalystcompound in the liquid (not including the support) is reduced by 70%from its initial concentration.

[0241] In one embodiment, the catalyst compounds can be added to theslurry as a solution, slurry, or powder. The catalyst component slurryis prepared prior to its use in the polymerization process of theinvention or the catalyst component slurry may be prepared in-line.

[0242] In one embodiment, the slurry is prepared by combining thecatalyst components, such as for example the catalyst or supportedcatalyst and the support and activator or supported activator, all atonce. In another embodiment, the slurry is prepared by first adding asupport material, then adding the combination of a catalyst and anactivator component.

[0243] In another embodiment the slurry comprises a supported activatorand at least one catalyst compound where the catalyst compound iscombined with the slurry as a solution. A preferred solvent is mineraloil.

[0244] In a another embodiment, alumoxane, preferably methyl alumoxaneor modified methyl alumoxane, is combined with a support such ascalcined silica or fumed silica to form a supported activator, thesupported activator is then dispersed in a liquid, such as degassedmineral oil, and then one or more catalyst compounds are added to thedispersion and mixed to form the catalyst component slurry. The catalystcompounds are preferably added to the dispersion as a solid, powder,solution or a slurry, preferably a slurry of mineral oil. If more thanone catalyst compound is added to the dispersion, the catalyst compoundscan be added sequentially, or at the same time.

[0245] In another embodiment the catalyst compound is added to theslurry in solid or powder form. In a preferred embodiment, a Group 15containing catalyst compound is added to the slurry in powder or solidform. In another preferred embodiment, [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂and or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂ is added to the slurry as apowder.

[0246] In a preferred embodiment the catalyst component slurry comprisesmineral oil and has a viscosity of about 130 to about 2000 cP at 20° C.,more preferably about 180 to about 1500 cP at 20° C. and even morepreferably about 200 to about 800 cP at 20° C. as measured with aBrookfield model LVDV-III Rheometer housed in a nitrogen purged drybox(in such a manner that the atmosphere is substantially free of moistureand oxygen, i.e. less than several ppmv of each). The catalyst componentslurries are made in a nitrogen purged drybox, and rolled in theirclosed glass containers until immediately before the viscositymeasurements are made, in order to ensure that they are fully suspendedat the start of the trial. Temperature of the viscometer is controlledvia an external temperature bath circulating heat transfer fluid intothe viscometer. The rheometer was fitted with the appropriate spindlefor the test material as specified in the unit's application guide.Typically, a SC4-34 or SC4-25 spindle was used. Data analysis wasperformed using Rheocalc V1.1 software, copyright 1995, BrookfieldEngineering Laboratories, preferably purchased and used with the unit.

[0247] In one embodiment, the catalyst component slurry comprises asupported activator and one or more or a combination of the catalystcompound(s) described in Formula I to IX above.

[0248] In another embodiment, the catalyst component slurry comprises asupported activator and one or more or a combination of the Group 15catalyst compound(s) represented by Formula I or II described above.

[0249] In another embodiment, the catalyst component slurry comprises asupported activator and one or more or combination of the bulky ligandcatalyst compound(s) represented by Formula III to VI described above.

[0250] In another embodiment, the slurry comprises supported activator,a Group 15 catalyst compound(s) represented by Formula I or II describedabove, and a the bulky ligand catalyst compound(s) represented byFormula III to VI

[0251] In another embodiment, the slurry comprises supported alumoxaneand [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH MBz₂ where M is a Group 4 metal, each Bzis a independently a benzyl group and Me is methyl.

[0252] In another embodiment, the slurry comprises a supportedalumoxane, a Group 15 catalysts compound and one of the following:bis(n-propyl cyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or (tetramethylcyclopentadienyl) (n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium or titanium and Xis chlorine, bromine, or fluorine.

[0253] In the polymerization process of the invention, described below,any of the above described catalyst component containing slurries may becombined with any of the catalyst component containing solutionsdescribed below. In addition, more than one catalyst componentcontaining slurry may be utilized.

[0254] B. Catalyst Component Solution

[0255] In one embodiment, the catalyst component solution includes acatalyst compound. In another embodiment, the solution also includes anactivator in addition to the catalyst compound.

[0256] The solution used in the process of this invention is typicallyprepared by dissolving the catalyst compound and optional activators ina liquid solvent. The liquid solvent is typically an alkane, such as aC₅ to C₃₀ alkane, preferably a C₅ to C₁₀ alkane. Cyclic alkanes such ascyclohexane and aromatic compounds such as toluene may also be used. Inaddition, mineral oil may be used as a solvent. The solution employedshould be liquid under the conditions of polymerization and relativelyinert. In one embodiment, the liquid utilized in the catalyst compoundsolution is different from the diluent used in the catalyst componentslurry. In another embodiment, the liquid utilized in the catalystcompound solution is the same as the diluent used in the catalystcomponent solution.

[0257] In a preferred embodiment the ratio of metal in the activator tometal in the catalyst compound in the solution is 1000:1 to 0.5:1,preferably 300:1 to 1:1, more preferably 150:1 to 1:1.

[0258] In a preferred embodiment, the activator and catalyst compound ispresent in the solution at up to about 90 wt %, preferably at up toabout 50 wt %, preferably at up to about 20 wt %, preferably at up toabout 10 wt %, more preferably at up to about 5 wt % , more preferablyat less than 1 wt %, more preferably between 100 ppm and 1 wt % basedupon the weight of the solvent and the activator or catalyst compound.

[0259] In one embodiment, the catalyst component solution comprises anyone of the catalyst compounds described in Formula I to IX above.

[0260] In another embodiment, the catalyst component solution comprisesa Group catalyst compound represented by Formula I or II describedabove.

[0261] In another embodiment, the catalyst component solution comprisesa bulky ligand catalyst compound represented by Formula III to VIdescribed above.

[0262] In a preferred embodiment the solution comprisesbis(n-propylcyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is a Group 4 metal, preferablyzirconium, hafnium or titanium and X is chlorine, bromine, or fluorine.

[0263] In the polymerization process of the invention, described below,any of the above described catalyst component containing solution(s) maybe combined with any of the catalyst component containingslurry/slurries described above. In addition, more than one catalystcomponent containing solution may be utilized.

[0264] C. Catalyst Compositions

[0265] The catalyst composition of the invention is formed by combiningany one of the catalyst component slurries with any one of the catalystcomponent solutions described above. Generally, the catalyst componentslurry and the catalyst component solution are mixed in the process ofthe invention to form the final catalyst composition, which is thenintroduced into a polymerization reactor and combined with and one ormore olefins.

[0266] In one embodiment, the slurry contains at least one support andat least one activator, preferably a supported activator, and thesolution contains at least one catalyst compound.

[0267] In another embodiment, the catalyst component slurry contains asupport, and an activator and/or a supported activator, and the catalystcomponent solution contains at least one catalyst compound and at leastone activator.

[0268] In one embodiment, the slurry contains at least one support andat least one activator, preferably a supported activator, and thesolution contains one or more catalyst compound(s) and/or one or moreactivator compound(s).

[0269] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activator(s),and the catalyst component solution contains at least one catalystcompound.

[0270] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activator(s),and the catalyst component solution contains at least one catalystcompound and at least one activator.

[0271] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activator(s),and the catalyst component solution contains one or more catalystcompound(s) and/or one or more activator compound(s).

[0272] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator, and also contains acatalyst compound and/or a supported catalyst compound, and the catalystcomponent solution contains at least one catalyst compound.

[0273] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator, and also contains acatalyst compound and/or a supported catalyst compound, and the catalystcomponent solution contains at least one catalyst compound and at leastone activator.

[0274] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator, and also contains acatalyst compound and/or a supported catalyst compound, and the catalystcomponent solution contains one or more catalyst compound(s) and/or oneor more activator compound(s).

[0275] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator and more than onecatalyst compound(s) and/or supported catalyst compounds, and thecatalyst component solution contains at least one catalyst compound.

[0276] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator and more than onecatalyst compound(s) and/or supported catalyst compounds, and thecatalyst component solution contains at least one catalyst compound andat least one activator.

[0277] In another embodiment, the catalyst component slurry contains asupport, an activator and/or a supported activator and more than onecatalyst compound(s) and/or supported catalyst compounds, and thecatalyst component solution contains one or more catalyst compound(s)and/or one or more activator compound(s).

[0278] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activators andmore than one catalyst compound(s) and/or supported catalystcompound(s), and the catalyst component solution contains at least onecatalyst compound.

[0279] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activators andmore than one catalyst compound(s) and/or supported catalystcompound(s), and the catalyst component solution contains at least onecatalyst compound and at least one activator.

[0280] In another embodiment, the catalyst component slurry containsmore than one support(s), activator(s) and/or supported activators andmore than one catalyst compound(s) and/or supported catalystcompound(s), and the catalyst component solution contains one or morecatalyst compound(s) and/or one or more activator compound(s).

[0281] In one embodiment the catalyst composition, formed by combiningthe catalyst component slurry and the catalyst component solution, has aviscosity of about 130 to about 2000 cP at 20° C., more preferably about180 to about 1500 cP at 20° C. even more preferably about 200 to about800 cP at 20° C.

[0282] In another embodiment, the catalyst component solution comprises,up to 80 weight %, preferably up to 50 weight %, preferably up to 20weight %, preferably up to 15 weight %, more preferably between 1 to 10weight %, more preferably 3 to 8 weight % of the combination of thecatalyst component solution and the catalyst component slurry, basedupon the weight of the solution and the slurry. In another preferredembodiment, the catalyst component solution comprises mineral oil andcomprises up to 90 weight %, preferably up to 80 weight %, morepreferably between 1 to 50 weight %, and more preferably 1 to 20 weight% of the combination of the catalyst component solution and the catalystcomponent slurry, based upon the weight of the solution and the slurry.

[0283] In one embodiment, the catalyst component slurry is fed to thepolymerization reactor utilizing a slurry feeder. In another embodimentthe catalyst composition is fed to the polymerization reactor utilizinga slurry feeder. A slurry feeder, for example, is described U.S. Pat.No. 5,674,795, incorporated herein by reference.

[0284] In one embodiment, the catalyst component solution, comprising acatalyst compound, is contacted with the catalyst component slurry sothat at least 50% of the catalyst compound originally in the catalystcomponent solution is deposited in or on the support, preferably atleast 70%, preferably at least 75%, preferably at least 80%, morepreferably at least 90%, preferably at least 95%, preferably at least99%.

[0285] In another embodiment, the catalyst component solution comprisinga metallocene catalyst compound, is contacted with a catalyst componentslurry comprising a support and an activator, preferably a supportedactivator, to form an immobilized catalyst composition. Aftercontacting, all or substantially all, preferably at least 50% preferablyat least 70%, preferably at least 75%, preferably at least 80%, morepreferably at least 90%, preferably at least 95%, preferably at least99% of the catalyst compound from the catalyst component solution isdeposited in or on the support initially contained in the catalystcomponent slurry. In one embodiment, a catalyst compound will beconsidered to be in or on the support if the concentration of thecatalyst compound in the liquid portion of the combination is reducedover time after adding the catalyst compound from the solution. Thecatalyst concentration may be measured as described above.

[0286] In another embodiment, the supported activator is in a mineraloil that is then contacted with a metallocene catalyst solution prior tointroducing the catalyst composition to the reactor, preferably wherethe contacting takes place in-line.

[0287] In another embodiment, the immobilized catalyst compositionsystem or components thereof may be contacted with a carboxylate metalsalt as described in PCT publication WO 00/02930 and WO 00/0293 1, whichare herein incorporated by reference.

[0288] In another embodiment the solution comprises a catalyst compoundand the slurry comprises a supported activator, such as supportedalumoxane, and two or more catalyst compounds, that may be the same ordifferent from the catalyst compound in the solution. The two catalystcompounds may be added to the slurry before or after the supportedactivator. In a preferred embodiment the supported activator is added tothe liquid diluent first to form a slurry, then a catalyst compound isadded to the slurry, and thereafter another catalyst compound is addedto the slurry. The second catalyst is preferably added after the firstcatalyst compound and the supported activator have been contacted for atleast 1 minute, preferably at least 15 minutes, more preferably at least30 minutes, more preferably at least 60 minutes, more preferably atleast 120 minutes, more preferably at least 360 minutes.

[0289] In another embodiment the two catalyst compounds are added to theslurry at the same time, in the same or different solutions. In anotherembodiment, a catalyst compound is contacted with an unsupportedactivator prior to being placed in the slurry. In a preferredembodiment, the unsupported activator is a modified or unmodifiedalumoxane, such as methyl alumoxane.

[0290] In another embodiment, the catalyst compound may be added to thesolution or slurry in its constituent parts of metal compound andligands. For example, cyclopentadienyl groups such as substituted orunsubstituted cyclopentadiene, indene, fluorene groups and metalcompounds such as zirconium tetrahalide may be added to the slurry orsolution or both and allowed to react therein. Likewise, one may alsoadd metal compounds and or ligands to the solution and or slurry thatalready contains catalyst compounds. The metal compounds and ligands maybe the same or different from the components of the catalyst compound inthe solution or slurry. In another embodiment ligands and/or metalcompounds may be added to both the solution and the slurry.

[0291] In another embodiment the catalyst composition comprises a“bisamide” catalyst compound (i.e., a bridged bis(arylamido) Group 4compounds described by D. H. McConville, et al., in Organometallics1195, 14, 5478-5480, or a bridged bis(amido) catalyst compoundsdescribed in WO 96/27439) combined with an activator, spray dried to apowder state, then combined with mineral oil to form a slurry. Thiscombination may then be combined with various catalyst componentsolutions to form a particularly effective multiple catalyst systems.Preferred catalyst compounds include those described above as bulkyligand metallocene catalysts. In another preferred embodiment the slurrycomprises a supported activator and the solution comprises a catalystcompound. The catalyst compounds may be selected from various catalystcompounds described above including bulky ligand metallocenes.

[0292] In another embodiment, the slurry comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,where each Bz is independently a benzyl group, Me is methyl, and thesolution comprises bis(n-propyl cyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium ortitanium and X is chlorine, bromine, or fluorine.

[0293] In another embodiment, the solution comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,where each Bz is independently a benzyl group, Me is methyl, and theslurry comprises: 1) supported alumoxane, and 2) bis(n-propylcyclopentadienyl)-MX₂,pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium ortitanium and X is chlorine, bromine, or fluorine.

[0294] In another embodiment, the slurry comprises: 1) a supportedalumoxane, 2) bis(n-propyl cyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium ortitanium and X is chlorine, bromine, or fluorine, and 3)[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,and the solution comprises a bulky ligand metallocene compound.

[0295] In another embodiment, the slurry comprises mineral oil and aspray dried catalyst compound. In another embodiment, the spray driedcatalyst compound is a Group 15 containing metal compound. In apreferred embodiment, the spray dried catalyst compound comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBZ₂.

[0296] In another embodiment, the catalyst compound and the supportedactivator may be combined before being combined with the slurry diluentor after.

[0297] In another embodiment the solution comprises a catalyst compoundof bis-indenyl zirconium dichloride, bis(n-propyl cyclopentadienyl)zirconium dichloride,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride, or a mixture thereof.

[0298] In another embodiment, a first catalyst compound is combined witha supported activator in the slurry, and a second catalyst compound andan activator are combined in the solution and thereafter the two aremixed in line. In another embodiment, the one activator is an alumoxaneand the other activator is a boron based activator.

[0299] In another embodiment the slurry comprises mineral oil, spraydried [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, and the solution comprisesbis(n-propyl cyclopentadienyl) zirconium dichloride.

[0300] In a one embodiment of this invention the slurry comprisessupported activator and a catalyst compound and the solution comprises acatalyst compound different in some way from the catalyst compound inthe slurry. For example, the slurry catalyst compound could be acompound represented by the Formula I or II described above, while thesolution catalyst compound could be a catalyst compound described byFormula III, IV, V, VI, or VII, or vice versa.

[0301] In another embodiment, if a bimodal polymer product were desired,one could mix a first catalyst compound with an activator in the slurry,then on-line add a solution of a different catalyst compound that iscapable of being activated by the same activator. Since the two catalystcompounds are introduced into the feed line independently, it will beeasier to control the amount of the two species in the final bimodalproduct, assuming that each catalyst produces at least one species ofpolymer.

[0302] In another embodiment, a Group 15 metal containing compound and abulky ligand metallocene catalyst compound are combined with supportedalumoxane in the process of this invention. Typically the two catalystcompounds are combined in the slurry with the supported alumoxane andthe solution will comprise a trim solution of one or the other of thetwo catalyst compounds.

[0303] In another embodiment, [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂, andbis(n-propyl cyclopentadienyl) zirconium dichloride are combined withsupported methyl alumoxane in the process of this invention. Typicallythe two catalyst compounds are combined in the slurry with the supportedalumoxane and the solution will comprise one or the other of the twocatalyst compounds. The solution is preferably used as a trim solutionto regulate the product formed in the reactor by varying the amount ofsolution combined with the slurry on-line, i.e. to trim the mix. In oneembodiment this catalyst combination is then used to polymerizeolefin(s), preferably ethylene, at a polymerization temperature of 80 to110° C. and in the presence of little or no comonomer(s) for examplehexene.

[0304] In another embodiment the slurry concentration is maintained atgreater than 0 to 90 wt % solids, more preferably 1 to 50 wt %, morepreferably 5 to 40 wt %, even more preferably 10 to 30 wt %, based uponthe weight of the slurry. In another preferred embodiment the activatoris present on the support at between about 0.5 to about 7 mmol/g,preferably about 2 to about 6 mmol/g, more preferably between about 4 toabout 5 mmol/g. In another preferred embodiment the total amount ofcatalyst compound present on the support, preferably a supportedactivator, is about 1 to about 40 μmol/g, preferably about 10 to about38 μmol/g, more preferably 30 to 36 μmol/g.

[0305] In one embodiment the final mole ratio (i.e. after combination ofthe solution and the slurry) of the metal of the catalyst compounds andthe metal of the activator is in the range of from about 1000:1 to about0.5:1 preferably from about 300:1 to about 1:1 more preferably fromabout 150:1 to about 1:1; for boranes, borates, aluminates, etc., theratio is preferably about 1:1 to about 10:1 and for alkyl aluminumcompounds (such as diethylaluminum chloride combined with water) theratio is preferably about 0.5:1 to about 10:1.

[0306] In one embodiment, the catalyst compound used in the slurry isnot soluble in the solvent used in the solution. By “not soluble” ismeant that the not more than 5 weight % of the material dissolves intothe solvent at 20° C. and less than 3 minutes of stirring, preferablynot more than 1 weight %, preferably not more than 0.1 weight %,preferably not more than 0.01 weight %. In a preferred embodiment, thecatalyst compound used in the slurry at least only sparingly soluble inan aromatic hydrocarbon. In a particularly preferred embodiment thecatalyst compound used in the slurry is not soluble in mineral oil,aromatic solvent or aliphatic hydrocarbon (pentane, heptane, etc.).

[0307] D. Delivery of the Catalyst Composition

[0308] In the process of the invention, the catalyst component slurry iscombined with and/or reacted with the catalyst component solution toform a catalyst composition in-line. The catalyst composition so formedis then is introduced into the polymerization reactor. Generally thecatalyst composition is introduced to the reactor utilizing a catalystfeed system which includes a catalyst component slurry holding vessel, acatalyst component solution holding vessel, and a slurry feeder.

[0309] Referring to FIG. 1, in one embodiment, the catalyst componentslurry, preferably a mineral oil slurry including at least one supportand at least one activator, preferably at least one supported activator,and optional catalyst compound(s) is placed in a vessel (A). In apreferred embodiment (A) is an agitated holding tank designed to keepthe solids concentration homogenous. The catalyst component solution,prepared by mixing a solvent and at least one catalyst compound and/oractivator, is placed in a vessel (C). The catalyst component slurry isthen combined in-line with the catalyst component solution to form afinal catalyst composition. A nucleating agent, such as silica, alumina,fumed silica or any other particulate matter (B) may be added to theslurry and/or the solution in-line or in the vessels (A) or (C).Similarly, additional activators or catalyst compounds may be addedin-line. The catalyst component slurry and solution are preferably mixedin-line at some point (E) for a period of time. For example, thesolution and slurry may be mixed by utilizing a static mixer or anagitating vessel. The mixing of the catalyst component slurry and thecatalyst component solution should be long enough to allow the catalystcompound in the catalyst component solution to disperse in the catalystcomponent slurry such that the catalyst component, originally in thesolution, migrates to the supported activator originally present in theslurry. The combination thereby becomes a uniform dispersion of catalystcompounds on the supported activator forming the catalyst composition ofthe invention. The length of time that the slurry and the solution arecontacted is typically up to about 120 minutes, preferably about 1 toabout 60 minutes, more preferably about 5 to about 40 minutes, even morepreferably about 10 to about 30 minutes.

[0310] In another embodiment, an aluminum alkyl, an ethoxylated aluminumalkyl, an alumoxane, an anti-static agent or a borate activator, such asa C₁ to C₁₅ alkyl aluminum (for example tri-isobutyl aluminum, trimethylaluminum or the like), a C₁ to C₁₅ ethoxylated alkyl aluminum or methylalumoxane, ethyl alumoxane, isobutylalumoxane, modified alumoxane or thelike are added to the mixture of the slurry and the solution in line.The alkyls, antistatic agents, borate activators and/or alumoxanes maybe added (F), directly to the combination of the solution and theslurry, or may be added via an additional alkane (such as isopentane,hexane, heptane, and or octane) carrier stream (G). Preferably, theadditional alkyls, antistatic agents, borate activators and/oralumoxanes are present at up to about 500 ppm, more preferably at about1 to about 300 ppm, more preferably at 10 to about 300 ppm, morepreferably at about 10 to about 100 ppm. Preferred carrier streamsinclude isopentane and or hexane. The alkane may be added (G) to themixture of the slurry and the solution, typically at a rate of about 0.5to about 60 lbs/hr (27 kg/hr). Likewise carrier gas, such as nitrogen,argon, ethane, propane and the like may be added in-line (H) to themixture of the slurry and the solution. Typically the carrier gas may beadded at the rate of about 1 to about 100 lb/hr (0.4 to 45 kg/hr),preferably about 1 to about 50 lb/hr (5 to 23 kg/hr), more preferablyabout 1 to about 25 lb/hr (0.4 to 11 kg/hr).

[0311] In another embodiment, a liquid carrier stream is introduced intothe combination of the solution and slurry that is moving in a downwarddirection. The mixture of the solution, the slurry and the liquidcarrier stream may pass through an optional mixer or length of tube formixing before being contacted with a gaseous carrier stream.

[0312] Similarly, hexene (or other alpha-olefin or diolefin) may beadded in-line (J) to the mixture of the slurry and the solution. Theslurry/solution mixture is then preferably passed through an injectiontube (O) to the reactor (Q). In some embodiments, the injection tube mayaerosolize the slurry/solution mixture. In a preferred embodiment theinjection tube has a diameter of about {fraction (1/16)} inch to about ½inch (0.16 cm to 1.27 cm), preferably about {fraction (3/16)} inch toabout ⅜ inch (0.5 cm to 0.9 cm), more preferably ¼ inch to about ⅜thsinch (0.6 cm to 0.9 cm).

[0313] In one embodiment cycle gas (also called re-cycle gas) isintroduced into the support tube (S), in another embodiment monomer gas,such as ethylene gas, is introduced into the support tube. Nucleatingagents (K), such as fumed silica, can be added directly in to thereactor.

[0314] In another embodiment a plenum may be used in this invention. Aplenum is a device used to create a particle lean zone in a fluidizedbed gas-phase reactor, as described in detail in U.S. Pat. No. 5,693,727which is incorporated herein by reference. A plenum may have one, two,or more injection nozzles.

[0315] In another embodiment when a metallocene catalyst or othersimilar catalyst is used in the gas phase reactor, oxygen and orfluorobenzene can be added to the reactor directly or to the recycle gasto affect the polymerization rate. Thus, when a metallocene catalyst(which is sensitive to oxygen or fluorobenzene) is used in combinationwith another catalyst (that is not sensitive to oxygen) in a gas phasereactor, oxygen can be used to modify the metallocene polymerizationrate relative to the polymerization rate of the other catalyst. Anexample of such a catalyst combination is bis(n-propyl cyclopentadienyl)zirconium dichloride and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, where Me ismethyl or bis(indenyl) zirconium dichloride and[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂, where Me is methyl. For example if theoxygen concentration in the nitrogen feed is altered from 0.1 ppm to 0.5ppm, significantly less polymer from the bisindenyl ZrCl₂ will beproduced and the relative amount of polymer produced from the[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂ is increased. WO/09328 discloses theaddition of water and or carbon dioxide to gas phase polymerizationreactors.

[0316] In another embodiment, referring still to FIG. 1, the slurrycomprising mineral oil, at least one catalyst compound, a support and anactivator is mixed in and/or introduced from (A). The catalyst componentsolution comprising a solvent, such as toluene, hexane, mineral oil ortetrahydrofuran, and a catalyst compound and/or an activator is mixed inand/or introduced from (C). Nucleating agent (B) and (K), such as fumedsilica, may be added on line at one or more positions and may be wet ordry. The slurry and the solution are combined and typically mixed at(E). Optional light alkyls (F), such as triisobutyl aluminum, analumoxane, modified methylalumoxane and/or trimethyl aluminum, may beadded in line directly to the combination or via an alkane, such asisopentane, feed (G). Nitrogen (H) and/or olefin, such as hexene, (J)may also be added in line. The combination may then be injected throughan injection tube (O) (such as a ⅛ inch (0.3cm) tube) into a gas phasereactor (Q). The injection tube (O) may be supported inside a largersupport tube (S), such as a 1 inch (2.54 cm) tube. Oxygen can be addeddirectly to the reactor (Q) or to the recycle gas (P) to alter theactivity of one or more catalysts. (R) is flow (monomer, recycle gas,alkane) to the support tube (S).

[0317] In another embodiment, catalyst ball formation and or generalnozzle fouling were reduced by first feeding isopentane carrier from thefeed line (G) into the combination of the solution and the slurry,thereafter the combination of the solution slurry and isopentanepreferably moves in a vertical orientation with a downward flow into thereactor using a nitrogen sweep (H) to disperse the isopentane/slurrymixture into the reactor.

[0318] The catalyst injection tube passes into the reactor through acompressed chevron packing and extends into the fluid bed a distance ofabout 0.1 inch to 10 feet (0.25 cm to 3.1 m), preferably about 1 inch to6 ft (2.5 cm to 1.8 m), and more preferably about 2 inches to 5 feet (5cm to 1.5 m). Typically, the depth of insertion depends on the diameterof the reactor and typically extends in about {fraction (1/20)} to ½ ofthe reactor diameter, preferably about {fraction (1/10)}th to ½ and morepreferably about ⅕th to ⅓rd of the reactor diameter. The end of the tubemay be cut perpendicular to the axis to create a nozzle cone or pointwith an angle ranging from 0 to 90 degrees, preferably ranging fromabout 10 to 80 degrees. The lip of the hole can be taken to a newknife-edge. The tube can be positioned to reduce resin adhesion orcoated with an antifouling or antistatic compound. The tube can also becut diagonally at an angle simply from about 0 to 80 degrees off theaxial line of the tube, preferably about 0 to 60 degrees. The opening ofthe tube can be the same as the bore of the tube or expanded ordiminished to create a nozzle, with sufficient pressure drop andgeometry to provide a dispersed spray of a solution slurry and or powderinto the reactor, preferably into the fluid bed.

[0319] The injection tube can optionally be supported inside a structurewithin the fluid bed to provide structural integrity. This support tubeis typically a heavy walled pipe with an internal diameter of from about¼ inch to about 5 inches (0.64 cm to 12.7 cm), preferably about ½ inchto about 3 inches (1.3 cm to 7.6 cm), and more preferably about ¾ inchto about 2 inches (1.9 cm to 5 cm). The support tube preferably extendsthrough the reactor wall to approximately the length of the injectiontube, allowing the injection tube to end just inside the end of thesupport tube or to extend past it up to about 10 inches (25.4 cm).Preferably, the injection tube extends about 0.5 to 5 inches (1.8 cm to12.7 cm) beyond the end of the support tube and more preferably about 1to 3 inches (2.5 cm to 7.6 cm). The end of the support tube in thereactor may be cut flat and perpendicular to the axis of the tube orpreferably, may be tapered at an angle ranging from about 10 to 80degrees. The end of the support tube may be polished or coated with ananti-static or anti-fouling material.

[0320] A purge flow of fluid (R) (typically fresh monomer, ethylene,hexane, isopentane, recycle gas, and the like) is preferably introducedfrom outside the reactor down the support tube to aid in dispersion ofthe catalyst composition allowing the production of resin granularparticles of good morphology with decreased agglomeration and an APS(average particle size) in the range of about 0.005 to 0.10 inches (0.01cm to 0.3 cm). The purge flow of fluid helps minimize fouling of the endof the catalyst injection tube and support tubes. The fluid introducedto the support tube may comprise hydrogen; olefins or diolefins,including but not limited to C₂ to C₄₀ alpha olefins and C₂ to C₄₀diolefins, ethylene, propylene, butene, hexene, octene, norbornene,pentene, hexadiene, pentadiene, isobutylene, octadiene, cyclopentadiene,comonomer being used in the polymerization reaction, hydrogen; alkanes,such C₁ to C₄₀ alkanes, including but not limited to isopetane, hexane,ethane, propane, butane, and the like; mineral oil, cycle gas with orwithout condensed liquids; or any combination thereof. Preferably thesupport tube flow is fresh ethylene or propylene that may be heated. Inaddition, an alkane, such as for instance isopentane or hexane, can beincluded in the flow at the level ranging from about 0.001 wt %. toabout 50% of the flow. The alkane can be dispersed in the flow and mayexist as dispersed liquid droplets or be vaporized at the exit of thesupport tube. The presence of liquid may reduce fouling at the exit.

[0321] The flow rate of fluid in the support tube ranges from about 5 to10,000 pph and is somewhat dependent upon the reactor size. The linearvelocity of the fluid in the support tube ranges from about 10 to 500ft/sec (11 to 549 km/hr), preferably about 20 to 300 ft/sec (22 to 329km/hr) and more preferably about 30 to 200 ft/sec (33 to 219 km/hr).

[0322] Alternatively, the exit of the support tube may be fashioned as anozzle at the end to form a jet or dispersion of gas to aid in thedistribution of the catalyst composition. In one embodiment, theinternal diameter of the support tube is reduced gradually by about 3 to80% at the end, preferably about 5 to 50% in a taper to create a nozzleto accelerate to and or disperse the fluid flow. The insertion of theinjection tube is not impacted by the internal taper of the supporttube.

[0323] In another embodiment of the invention the contact time of theslurry and the solution can be varied to adjust or control formation ofthe active catalyst complex. The contact time of the slurry and thesolution is preferably in the range of from 1 minute to 120 minutes,preferably in the range of from 2 minutes to 60 minutes, preferably 5minutes to 45 minutes, more preferably from about 10 minutes to about 30minutes.

[0324] In another embodiment, the contact temperature of the slurry andthe solution is in the range of from 0° C. to about 80° C., preferablyfrom about 0° C. to about 60° C., more preferably from about 10° C. toabout 50° C. and most preferably from about 20° C. to about 40° C.

[0325] In another embodiment, the invention provides introducing theimmobilized catalyst system in the presence of a mineral oil or asurface modifier or a combination thereof as described in PCTpublication WO 96/11960 and U.S. Ser. No. 09/113,261 filed Jul. 10,1998, which are herein fully incorporated by reference. In anotherembodiment a slurry or surface modifier, such as an aluminum stearate inmineral oil) is introduced (T) into the reactor with the combination ofthe slurry and the solution. In another embodiment the surface modifier,such as aluminum stearate, was added into the slurry vessel (A).

[0326] In another embodiment the one or all of the catalysts arecombined with up to 6 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) or ananti-static agent based upon the weight of the catalyst, any support andthe stearate or anti-static agent, preferably 2 to 3 weight %. In oneembodiment, a solution or slurry of the metal stearate or anti-staticagent is fed into the reactor. The stearate or anti-static agent may becombined with the slurry (A) or the solution (C) or may be co-fed (R)with the combination of the slurry and the solution. In a preferredembodiment the catalyst compounds and or activators are combined withabout 0.5 to about 4 weight % of an antistat, such as a methoxylatedamine, such as Witco's Kemamine AS-990 from ICI Specialties inBloomington Del.

[0327] In another embodiment the catalyst system or the componentsthereof are combined with benzil, xylitol, Irganox™ 565, sorbitol or thelike and then fed into the reactor. These agents may be combined withthe catalyst compounds and/or activators or may be fed into the reactorin a solution with or without the catalyst system or its components.Similarly these agents may be combined with the slurry (A) or thesolution (C) or may be co-fed (R) with the combination of the slurry andthe solution.

[0328] In another embodiment the process of this invention may furthercomprise additional solutions and slurries. For example, in a preferredembodiment a slurry can be combined with two or more solutions havingthe same or different catalyst compounds and or activators. Likewise,the solution may be combined with two or more slurries each having thesame or different supports, and the same or different catalyst compoundsand or activators. Similarly the process of this invention may comprisetwo or more slurries combined with two or more solutions, preferablyin-line, where the slurries each comprise the same or different supportsand may comprise the same or different catalyst compounds and oractivators and the solutions comprise the same or different catalystcompounds and or activators. For example, the slurry may contain asupported activator and two different catalyst compounds, and twosolutions, each containing one of the catalysts in the slurry, are eachindependently combined, in-line, with the slurry.

[0329] E. Use of Catalyst Composition to Control Product Properties

[0330] The timing, temperature, concentrations, and sequence of themixing of the solution, the slurry and any optional added materials(nucleating agents, catalyst compounds, activators, etc) described abovecan be used to alter product properties. The melt index, relative amountof polymer produced by each catalyst, and other properties of thepolymer produced may also be changed by manipulating process parameterswhich include manipulating hydrogen concentration in the polymerizationsystem or by:

[0331] 1) changing the amount of the first catalyst in thepolymerization system, and/or

[0332] 2) changing the amount of the second catalyst in thepolymerization system, and/or

[0333] 3) changing the hydrogen concentration in the polymerizationprocess; and/or

[0334] 4) changing the relative ratio of the catalyst in thepolymerization process (and optionally adjusting their individual feedrates to maintain a steady or constant resin production rate); and/or

[0335] 5) changing the amount of liquid and/or gas that is withdrawnand/or purged from the process; and/or

[0336] 6) changing the amount and/or composition of a recovered liquidand/or recovered gas returned to the polymerization process, saidrecovered liquid or recovered gas being recovered from polymerdischarged from the polymerization process; and/or

[0337] 7) using a hydrogenation catalyst in the polymerization process;and/or

[0338] 8) changing the polymerization temperature; and/or

[0339] 9) changing the ethylene partial pressure in the polymerizationprocess; and/or

[0340] 10) changing the ethylene to comonomer ratio in thepolymerization process; and/or

[0341] 11) changing the activator to transition metal ratio in theactivation sequence; and/or

[0342] 12) changing the relative feed rates of the slurry and/orsolution; and/or

[0343] 13) changing the mixing time, the temperature and or degree ofmixing of the slurry and the solution in-line; and/or

[0344] 14) adding different types of activator compounds to thepolymerization process; and/or

[0345] 15) adding oxygen or fluorobenzene or other catalyst poison tothe polymerization process.

[0346] For example to alter the flow index and or melt index of apolymer produced according to the invention using a slurry of supportedmethylalumoxane and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and a solution ofbis(n-propyl cyclopentadienyl) zirconium dichloride one can alter thetemperature of the reaction in the polymerization reactor, one can alterthe concentration of hydrogen in the reactor, or one can alter theconcentration of the bis(n-propyl cyclopentadienyl) zirconium dichloridein the solution prior to contacting the solution with the slurry, or onecan alter the relative feed rate of the catalyst component solutionand/or the catalyst component slurry.

[0347] In a preferred embodiment, the flow index (I₂₁—measured accordingto ASTM D-1238, Condition E, at 190° C.) of the polymer product ismeasured at regular intervals and one of the above factors, preferablytemperature, catalyst compound feed rate, the ratio of the two or morecatalysts to each other, monomer partial pressure, oxygen concentration,and or hydrogen concentration, is altered to bring the flow index to thedesired level, if necessary. Preferably the samples for flow indexmeasurements are melt-homogenized by extruding in an extruder that isequipped with either a single screw, preferably with a mixing head, or atwin screw, to make either tape or strand(s). The tape and or strandsare typically cut into small pieces for flow property measurements.

[0348] In an embodiment, a polymer product property is measured in-lineand in response the ratio of the catalysts being combined is altered. Inone embodiment, the molar ratio of the catalyst compound in the catalystcomponent slurry to the catalyst compound in the catalyst componentsolution, after the slurry and solution have been mixed to form thefinal catalyst composition, is 500:1 to 1:500, preferably 100:1 to1:100, more preferably 50:1 to 1:50 and most preferably 40:1 to 1:10. Inanother embodiment, the molar ratio of a Group 15 catalyst compound inthe slurry to a bulky ligand metallocene catalyst compound in thesolution, after the slurry and solution have been mixed to form thecatalyst composition, is 500:1, preferably 100:1, more preferably 50:1,more preferably 10:1 and even more preferably 5:1. Preferably, theproduct property measured is the polymer product's flow index, meltindex, density, MWD, comonomer content and combinations thereof. Inanother embodiment, when the ratio of the catalyst compounds is altered,the introduction rate of the catalyst composition to the reactor, orother process parameters, is altered to maintain a desired productionrate.

[0349] Likewise, the support architecture, the number of functionalgroups on the support (such as —OH groups on silica) the activatorloading and the pre-impregnated catalyst loading can also affect theproduct formed.

[0350] Similarly, altering the ethylene partial pressure can alterproduct properties. For example in a system where the solution comprisedbis(n-propyl cyclopentadienyl) zirconium dichloride and the slurrycomprised [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ and supported methylalumoxane, increasing the ethylene partial pressure in the gas phasereactor from 220 to 240 psi (1.5-1.7 MPa) increased the Flow Index from100 to over 700 dg/min.

[0351] While not wishing to be bound by or limited to any theory, theinventors believe, that the processes described herein immobilize thesolution catalyst compound in and on a support, preferably a supportedactivator. The in-line immobilization techniques described hereinpreferably result in a supported catalyst system that when introduced tothe reactor provides for better particle morphology, bulk density,and/or higher catalyst activities and without the need for additionalequipment in order to introduce catalyst compound solution into areactor, particularly a gas phase or slurry phase reactor. It is knownin the art that typical support techniques for supporting, metallocenecatalyst compounds results in lower overall productivity of the formedsupported catalysts. In some instances the supporting process in factrenders certain of these catalyst compounds useless in commercialpolymerization processes that especially prefer the utilization ofsupported catalysts. This is particularly true when comparingintroducing an unsupported catalyst system into a gas phase processversus a conventional supported catalyst system. By conventionalsupported catalysts system it is meant those supported catalyst systemsthat are formed by contacting a support material, an activator and acatalyst compound in various ways under a variety of conditions outsideof a catalyst feeder apparatus. Examples of conventional methods ofsupporting metallocene catalyst systems are described in U.S. Pat. Nos.4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,5,723,402, 5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and5,939,348 and U.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and788,736 filed Jan. 23, 1997 and PCT publications WO 95/32995, WO95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494. It was alsosurprisingly discovered that catalyst systems not commerciallysupportable in a gas phase process in particular were found to be usefulwhen immobilized using the process of the invention.

[0352] VI. Polymerization Process

[0353] The catalyst systems prepared and the method of catalyst systemaddition described above are suitable for use in any prepolymerizationand/or polymerization process over a wide range of temperatures andpressures. The temperatures may be in the range of from −60° C. to about280° C., preferably from 50° C. to about 200° C., and the pressuresemployed may be in the range from 1 atmosphere to about 500 atmospheresor higher.

[0354] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0355] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0356] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0357] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 3 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0358] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0359] In an embodiment, the mole ratio of comonomer to ethylene,C_(x)/C₂, where C_(x) is the amount of comonomer and C₂ is the amount ofethylene is between about 0.001 to 0.200 and more preferably betweenabout 0.002 to 0.008.

[0360] In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene catalysts as described in U.S. Pat.Nos. 5,296,434 and 5,278,264, both of which are herein incorporated byreference.

[0361] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0362] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 600 psig (4138 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0363] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0364] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0365] In a preferred embodiment, the reactor utilized in the presentinvention is capable of and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0366] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0367] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. Nos. 4,613,484 and5,986,021, which are herein fully incorporated by reference.

[0368] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0369] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998, 5,589,555 and 5,977,251 and PCT WO99/32525 and PCT WO 99/40130, which are fully incorporated herein byreference

[0370] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the presence ofa bulky ligand metallocene catalyst system of the invention and in theabsence of or essentially free of any scavengers, such astriethylaluminum, trimethylalumium, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. Nos. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

[0371] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of themetallocene catalyst systems of the invention described above prior tothe main polymerization. The prepolymerization can be carried outbatchwise or continuously in gas, solution or slurry phase including atelevated pressures. The prepolymerization can take place with any olefinmonomer or combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

[0372] In one embodiment, toluene is not used in the preparation orpolymerization process of this invention.

[0373] VII. Polymer Products

[0374] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, multimodal or bimodalhigh molecular weight polyethylenes, polypropylene and polypropylenecopolymers.

[0375] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86 g/cc to 0.97 g/cc, depending on the desireduse. For some applications a density in the range of from 0.88 g/cc to0.920 g/cc is preferred while in other applications, such as pipe, filmand blow molding, a density in the range of from 0.930 g/cc to 0.965g/cc is preferred. For low density polymers, such as for filmapplications, a density of 0.910 g/cc to 0.940 g/cc is preferred.Density is measured in accordance with ASTM-D1238.

[0376] The polymers produced by the process of the invention may have amolecular weight distribution, a ratio of weight average molecularweight to number average molecular weight (M_(w)/M_(n)), of greater than1.5 to about 70. In some embodiments the polymer produced has a narrowM_(w)/M_(n) of about 1.5 to 15, while in other embodiments the polymerproduced has an M_(w)/M_(n) of about 30 to 50. Also, the polymers of theinvention may have a narrow or broad composition distribution asmeasured by Composition Distribution Breadth Index (CDBI). Furtherdetails of determining the CDBI of a copolymer are known to thoseskilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference. In some embodiments the polymer produced may have a CDBI of80% or more or may have a CDBI of 50% or less.

[0377] The polymers of the invention in one embodiment have CDBI'sgenerally in the range of greater than 50% to 100%, preferably 99%,preferably in the range of 55% to 85%, and more preferably 60% to 80%,even more preferably greater than 60%, still even more preferablygreater than 65%.

[0378] In another embodiment, polymers produced using this inventionhave a CDBI less than 50%, more preferably less than 40%, and mostpreferably less than 30%.

[0379] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range from0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min toabout 100 dg/min, even more preferably from about 0.01 dg/min to about50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

[0380] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0381] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0382] In one embodiment the polymers produced by this invention have amultimodal molecular weight distribution (Mw/Mn) or, a typically,bimodal molecular weight distribution. In a preferred embodiment, thepolymer produced has a density of 0.93 to 0.96 g/cc, an MI (I₂) of0.03-0.10 g/10 min, an FI (I₂₁) of 4-12 g/10 min, an MFR (I₂₁/I₂) of80-180, an overall Mw of 200,000 to 400,000, an overall Mn of5,000-10,000 and an Mw/Mn of 20-50. Preferably the low molecular weightfraction (˜500-˜50,000) has a density of 0.935-0.975 g/cc and the highmolecular weight fraction (˜50,000-˜8,000,000) has a density of0.910-0.950 g/cc. These polymers are particularly useful for film andpipe, especially, for PE-100 pipe applications. More preferably, thisembodiment of the polymer has the following molecular weightdistribution (MWD) characteristics. The MWDs, as obtained from sizeexclusion chromatography (SEC), can be deconvoluted using the bimodalfitting program. The preferred split of the polymer, the ratio of Wt %of HMW fraction and the Wt % of LMW fraction, is 20-80 to 80-20, morepreferably 30-70 to 70-30, and even more preferably 40-60 to 60-40.Higher Wt % of HMW than LMW Wt % is preferred. The SEC curve can befurther analyzed to give percent of Wt %>1 MM, which is the weightpercent of the total MWD that has a molecular weight greater than 1million, and Wt %>100K, which is the weight percent of the total MWDthat is greater than 100,000 in molecular weight. The weight percentratio is simply Wt %>1 MM divided by Wt %>100K. 100,000 was used as anapproximate means of dividing the total MWD into a HMW (high molecularweight) and LMW (low molecular weight) region. This ratio gives a simplebut sensitive indication of the relative amount of the very highmolecular weight species in the HMW region of the MWD. The preferredembodiment of the polymer has the preferred range of weight percentration (WPR), higher than 10 but less than 30, preferably higher than 15but less than 25. The stability of blown bubble during film extrusion isfound to depend on this WPR as shown in the table below. A preferredcatalyst system to produce these polymers according to this inventioncomprises [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂ or[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ combined with bis(indenyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride or(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride, and supported methylalumoxane. HMW HMW wt % Bubble Sample FIMI MFR Mw % Split Wt % > 1 MM Wt % > 100 K Ratio Stability No. 1 8.320.051 167.3 605,500 53.5% 9.7% 41.8% 23% Poor No. 2 7.45 0.06 124584,000 50.1% 8.7% 41.7% 21% Good No. 3 7.99 0.047 168.7 549,900 53.3%8.7% 40.9% 21% Good No. 4 9.16 0.076 121.2 454,700 58.3% 7.5% 42.1% 18%Good No. 5 8.11 0.094 86.7 471,800 53.7% 6.6% 43.3% 15% Poor

[0383] A typical SEC curve of the embodiment of the polymer is shown inthe FIG. 5. Two distinctive peaks of HMW and LMW fractions can be seenwith the deconvoluted curves. LMW HMW Overall Mn: 3,231 91,514 8,076 Mw:12,307 505,322 291,217 Mw/Mn: 3.81 5.52 36.06 Wt %: 43.57% 56.43%

[0384] This multimodal or bimodal polymer is found to exhibit excellentbubble stability and good film extrusion characteristics. The polymerdemonstrated excellent draw-down characteristics and as thin as 0.35 milfilm was obtained. The film appearance rate was excellent with no speckof gels. The film dart impact strength was excellent suitable which issuitable for grocery sacks applications.

[0385] In another embodiment the polymer produced by this invention hasa bimodal molecular weight distribution (Mw/Mn). In a preferredembodiment, the polymer produced has a density of 0.93 to 0.97 g/cc, anMI (I₂) of 0.02-0.5 g/10 min, an FI (I₂₁) of 10-40 g/10 min, an MFR(I₂₁/I₂) of 50-300, an Mw of 100,000 to 500,000, an Mn of 8,000-20,000and an Mw/Mn of 10-40. These polymers are particularly useful for blowmolding applications. These bimodal polymers exhibited extraordinaryBent Strip ESCR (environmental stress crack resistance) performance,which far exceeds the performance of unimodal HDPE. Also, the blowmolded bottles trimmed easier and had opaque finish, which is preferredover translucent finish of unimodal HDPE.

[0386] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene or mixtures thereof produced by using two or moredifferent catalysts in the practice of this invention. Other propylenepolymers include propylene block or impact copolymers. Propylenepolymers of these types are well known in the art, see for example U.S.Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117, allof which are herein incorporated by reference.

[0387] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes produced via conventional Ziegler-Nattaand/or bulky ligand metallocene catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

[0388] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

[0389] In another embodiment, the polymer of the invention is made intoa pipe by methods known in the art. For pipe applications, the polymersof the invention have a I₂₁ of from about 2 to about 10 dg/min andpreferably from about 2 to about 8 dg/min. In another embodiment, thepipe of the invention satisfies ISO qualifications. In anotherembodiment, the present invention is used to make polyethylene pipehaving a predicted S-4 T_(c) for 110 mm pipe of less than −5° C.,preferably of less than −15° C and more preferably less than −40° C.(ISO DIS 13477/ASTM F1589).

[0390] In another embodiment, the polymer has an extrusion rate ofgreater than about 17 lbs/hour/inch of die circumference and preferablygreater than about 20 lbs/hour/inch of die circumference and morepreferably greater than about 22 lbs/hour/inch of die circumference

[0391] The polyolefins of the invention can be made into films, moldedarticles (including pipes), sheets, wire and cable coating and the like.The films may be formed by any of the conventional techniques known inthe art including extrusion, co-extrusion, lamination, blowing andcasting. The film may be obtained by the flat film or tubular processwhich may be followed by orientation in a uniaxial direction or in twomutually perpendicular directions in the plane of the film to the sameor different extents. Orientation may be to the same extent in bothdirections or may be to different extents. Particularly preferredmethods to form the polymers into films include extrusion or coextrusionon a blown or cast film line.

[0392] In another embodiment, the polymer of the invention is made intoa film by methods known in the art. For film application, the polymersof the invention have a I₂₁ of from about 2 to about 50 dg/min,preferably from about 2 to about 30 dg/min, even more preferably fromabout 2 to about 20 dg/min, still more preferably about 5 to about 15dg/min and yet more preferably from about 5 to about 10 dg/min.

[0393] The objects produced (such as films, pipes, etc) may furthercontain additives such as slip, antiblock, antioxidants, pigments,fillers, antifog, UV stabilizers, antistats, polymer processing aids,neutralizers, lubricants, surfactants, pigments, dyes and nucleatingagents. Preferred additives include silicon dioxide, synthetic silica,titanium dioxide, polydimethylsiloxane, calcium carbonate, metalstearates, calcium stearate, zinc stearate, talc, BaSO₄, diatomaceousearth, wax, carbon black, flame retarding additives, low molecularweight resins, hydrocarbon resins, glass beads and the like. Theadditives may be present in the typically effective amounts well knownin the art, such as 0.001 weight % to 10 weight %.

[0394] In another embodiment, the polymer of the invention is made intoa molded article by methods known in the art, for example, by blowmolding and injection-stretch molding. For molded applications, thepolymers of the invention have a I₂₁ of from about 20 dg/min to about 50dg/min and preferably from about 35 dg/min to about 45 dg/min.

[0395] Further, while not wishing to be bound by any theory, it isbelieved that the polymers produced by this invention have the uniqueadvantage of the two polymer products being so intimately blended thatthere is an even distribution of the two polymers across the polymerparticles as they exit the reactor. The unprocessed, untreated granularpolymer is referred to as neat polymer. The neat polymer is thenseparated into fractions by standard sieve sizes according to ASTM D1921 particle size (sieve analysis) of Plastic Materials, Method A orPEG Method 507. Sieve size Fraction Collected Fraction Name 10mesh >2000 μm Fraction 1 18 mesh 2000-1000 μm Fraction 2 35 mesh<1000-500 μm Fraction 3 60 mesh <500-250 μm Fraction 4 120 mesh <250-125μm Fraction 5 200 mesh/Pan <125 μm Fraction 6 Overall Fraction 6

[0396] The individual fractions (Fraction 2, 3, 4, 5) are then testedfor physical properties. Melt index is measured according to ASTM 1238,condition E, 190° C.

[0397] A unique attribute of the polymer produced herein is that themelt indices of the different fractions do not vary significantly. In apreferred embodiment the melt indices of Fractions 3, 4 and 5 do notvary by more than 40% relative, preferably by not more than 30%relative, preferably by not more than 10% relative, preferably by notmore than 8% relative, preferably by not more that 6% relative,preferably by not more than 4% relative. Relative means relative to themean of the values for Fractions 3, 4 and 5.

[0398] In another embodiment, fractions 2, 3, 4 and 5 comprise more than90% of the total weight of the resin sample; preferably fractions 2, 3and 4 comprise more than 90% of the total weight of the resin sample.

[0399] Another desirable attribute of the polymer produced herein isthat the Mw/Mn of the different fractions do not vary significantly. Ina preferred embodiment the Mw/Mn of Fractions 1, 4, 5 and 6 do not varyby more than 20% relative, preferably by not more than 10% relative,preferably by not more than 8% relative, preferably by not more than 6%relative, preferably by not more that 4% relative, preferably by notmore than 2% relative. In a preferred embodiment the Mw/Mn of Fractions1, 4 and 6 do not vary by more than 20% relative, preferably by not morethan 10% relative, preferably by not more than 8% relative, preferablyby not more than 6% relative, preferably by not more that 4% relative,preferably by not more than 2% relative. Relative means relative to themean of the values for Fractions 1, 4 and 6. In another preferredembodiment the Mw/Mn of Fractions 2, 3, 4 and 5 do not vary by more than20% relative, preferably by not more than 10% relative, preferably bynot more than 8% relative, preferably by not more than 6% relative,preferably by not more that 4% relative, preferably by not more than 2%relative. Relative means relative to the mean of the values forFractions 2, 3, 4 and 5. In a another preferred embodiment the Mw/Mn ofFractions 3, 4 and 5 do not vary by more than 20% relative, preferablyby not more than 10% relative, preferably by not more than 8% relative,preferably by not more than 6% relative, preferably by not more that 4%relative, preferably by not more than 2% relative. Relative meansrelative to the mean of the values for Fractions 3, 4 and 5. Mn and Mware measured by gel permeation chromatography on a waters 150° C. GPCinstrument equipped with differential refraction index detectors. TheGPC columns are calibrated by running a series of narrow polystyrenestandards and the molecular weights are calculated using broadpolyethylene standards National Bureau of Standards 1496 for the polymerin question.

[0400] In another preferred embodiment the polymer produced according tothis invention comprises 10-90 weight % of low molecular weight polymer(low is 50,000 or less preferably 40,000 or less), preferably 20 to 80weight %, more preferably 40-60 weight %, based upon the weight of thepolymer.

[0401] In one embodiment the fractions have the followingcharacteristics. Sieve Fraction Fraction size Collected Weight % I21 I5I2 Name  10 >2000 μm 0.5 Fraction 1 mesh  18 2000-1000 μm 1.02 23.9 0.750.14 Fraction 2 mesh  35 <1000-500 μm 15.11 37.6 1.18 0.22 Fraction 3mesh  60 <500-250 μm 44.05 41.0 1.28 0.20 Fraction 4 mesh 120 <250-125μm 33.62 40.8 .93 0.18 Fraction 5 mesh 200 <125 μm 5.70 Fraction 6 mesh/Pan Overall 100.0 41.6 1.18 0.23 Fraction 6

[0402] In another embodiment the polyolefin produced is found to have atleast two species of molecular weights present at greater than 20 weight% based upon the weight of the polymer.

[0403] In another embodiment of this invention the polymer produced isbi- or multi-modal (on the SEC graph). By bi- or multi-modal is meantthat the SEC graph of the polymer has two or more positive slopes, twoor more negative slopes, and three or more inflection points (aninflection point is that point where the second derivative of the curvebecomes negative) OR the graph has at least has one positive slope, onenegative slope, one inflection point and a change in the positive and ornegative slope greater than 20% of the slope before the change. Inanother embodiment the SEC graph has one positive slope, one negativeslope, one inflection point and an Mw/Mn of 10 or more, preferably 15 ormore, more preferably 20 or more. The SEC graph is generated by gelpermeation chromatography on a waters 150° C. GPC instrument equippedwith differential refraction index detectors. The columns are calibratedby running a series of narrow polystyrene standards and the molecularweights were calculated using Mark Houwink coefficients for the polymerin question.

[0404] The films produced using the polymers of this invention haveextremely good appearance properties. The films have a low gel contentand/or have good haze and gloss. In a preferred embodiment the 1 milfilm (1.0 mil=0.25 μm) has a 45° gloss of 7 or more, preferably 8 ormore as measured by ASTM D 2475. In a preferred embodiment the 1 milfilm (1.0 mil=25 μm) has a haze of 75 of less, preferably 70 or less asmeasured by ASTM D 1003, condition A.

[0405] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

EXAMPLES

[0406] Mn and Mw were measured by gel permeation chromatography on awaters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

[0407] Density was measured according to ASTM D 1505.

[0408] Melt Index (MI) and Flow Index (FI) I₂ and I₂₁ were measuredaccording to ASTM D-1238, Condition E, at 190° C.

[0409] Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as determinedby ASTM D-1238.

[0410] Weight % comonomer was measured by proton NMR.

[0411] MWD=M_(w)/M_(n)

[0412] Dart Impact was measured according to ASTM D 1709.

[0413] MD and TD Elmendorf Tear were measured according to ASTM D 1922.

[0414] MD and TD 1% Secant modulus were measured according to ASTM D882.

[0415] MD and TD tensile strength and ultimate tensile strength weremeasured according to ASTM D 882.

[0416] MD and TD elongation and ultimate elongation were measuredaccording to ASTM D 412.

[0417] MD and TD Modulus were measured according to ASTM 882-91

[0418] Haze was measured according to ASTM 1003-95, Condition A.

[0419] 45° gloss was measured according to ASTM D 2457.

[0420] BUR is blow up ratio.

[0421] “PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw”is parts per million by weight.

Example 1 Preparation of SMAO Supported Activator

[0422] For a 1 Kg batch, 1158.43 grams of 30 wt % MAO in toluene (7.3 wt% Al) available from Albemarle Corporation, Baton Rouge, La., and 2400grams of extra toluene are charged into an 8 liter mix tank equippedwith ribbon helical agitator. 984 grams of Davison 955-600 silica isadded to MAO in toluene solution at ambient temperature. A 10° C.exotherm occurs from reaction of the MAO with the hydroxyl groups. Theslurry mixes for 30 minutes at ambient temperature. Drying then occursby heating the mix tank jacket to about 70° C. and reducing pressure to0.00 mm/hg. As the slurry thickens the agitator rpm is reduced tominimum rotation, about 40-60 RPM. Then the rotation is slowly increased(to about 600 RPM) and the temperature is raised to 95° C. as the slurryturns to a dry powder. A nitrogen sweep (about 0.5 cc/min per gram ofsilica charged) can be used during the end of the drying step to helpremove toluene from the silica pores. The material is typically held at95° C. until toluene removal stops, and material temperature lines outnear jacket temperature. The material temperature does not change for atleast 30 minutes before the supported methylalumoxane (SMAO) isconsidered dry. Residual toluene is reduced to less than 2 wt % on thesolids.

Example 2 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor with Shorter ContactTime

[0423] Polymerization performance of in-line supported bis(n-propylcyclopentadienyl) zirconium dichloride (P-MCN) was evaluated in a 8 inch(20.3 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration is shown schematically in FIG. 2. P-MCN (1.7 umol/ml inhexane) was introduced in line at 0.65 g/hr. 0.5 weight % of TiBA inisopentane (200-250 cc/hr of isopentane carrier and 75-90 cc/hr of 0.5wt % TiBA) was introduced in line. Thereafter a slurry comprising Kaydolmineral oil and 16 weight % of SMAO produced in Example 1 (4.5 mmol/gsolids) was introduced in line and allowed to mix with the solution ofP-MCN and TiBA for 25-35 minutes. Following the mixer, the catalyst wasinjected using a standard ⅛ inch (0.32 cm) injection tube with 1.05 pphof N₂ blowback.

[0424] The catalyst was evaluated at LLDPE conditions, 75 C, 350 psig(2.4 MPa) total pressure, 120 psi (0.8 MPa) ethylene, 0.017 hexene-1comonomer to ethylene ratio. No hydrogen was fed to the reactor sincethis catalyst makes sufficient hydrogen to produce 2-5 dg/min melt indexpolymer under the conditions employed. The superficial gas velocity(SGV) was maintained at 1.54 ft/s (0.47 m/s) and the steady state bedweight at 27 lbs (12.3 kg). The reactor was operated continuously, i.e.for approximately 13 hours per day, generally holding bed weightconstant to yield a bed level near the top of the straight section.Where possible, the reactor was left closed overnight with the bed beingfluidized in a nitrogen atmosphere. TiBA (triisobutyl aluminum) inisopentane was fed as a scavenger at approximately 75 ppm in the bed togive catalyst productivity that is commercially relevant.

[0425] The product had a 6.1 dg/min (I2), 17.6 MFR and 0.93 g/ccdensity. The resin average particle size was 0.022 inches (0.056 cm)with 2.4 wt % fines (<120 mesh). The settled bulk density was 27.4lb/cu-ft. A residual zirconium of 0.66 ppm, aluminum of 33 ppm andsilica of 75 ppm was measured by ICP (Inductively Coupled Plasmaspectroscopy).

Example 3 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor with Longer ContactTime

[0426] Polymerization performance of in-line supported bis(n-propylcyclopentadienyl) zirconium dichloride (P-MCN) was evaluated in a 8 inch(20.3 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration is shown schematically in FIG. 3. P-MCN, fed at 0.56 g/hrwith 65-100 cc/hr of 0.5 wt % TIBA in isopentane upstream, was contactedwith 16 wt % SMAO (as produced in Example 1) in Kaydol mineral oilupstream of the 150 ml mixer. The solution and the slurry were allowedto mix for 90 to 130 minutes. 200-250 cc/hr of isopentane carrier wasused to sweep the catalyst exiting the mixer to the reactor. Followingthe mixer, catalyst was injected using a standard ⅛ inch (0.32 cm)injection tube with 1.1 pph N₂ blowback.

[0427] Catalyst was evaluated at LLDPE conditions, 75° C., 350 psig (2.4MPa) total pressure, 120 psi (0.8 MPa) ethylene, 0.017 hexene-1comonomer to ethylene ratio. No hydrogen was fed to the reactor sincethis catalyst makes sufficient hydrogen to produce 2-5 dg/min melt indexpolymer under the conditions employed. The superficial gas velocity(SGV) was maintained at 1.38 ft/s (0.42 m/s) and the steady state bedweight at 30.5 lbs (13.6 kg). The reactor was operated continuously for˜13 hours per day, generally holding bed weight constant to yield a bedlevel near the top of the straight section. Where possible, the reactorwas left closed overnight with the bed being fluidized in a nitrogenatmosphere. TIBA(triisobutyl alumium) in isopentane was fed as ascavenger at ˜75 ppm in the bed to give catalyst productivity that iscommercially relevant.

[0428] The product had a 5.3 dg/min (I₂), 18.9 MFR and 0.928 g/ccdensity. The resin average particle size was 0.021 inches (0.053 cm)with 2.8 wt % fines (<120 mesh). The settled bulk density was 26.0lb/cu-ft. A residual zirconium of 0.55 ppm, aluminum of 35 ppm andsilica of 78 ppm was measured by ICP.

[0429] The data for Examples 2 and 3 are summarized in Table 1. TABLE 18 INCH (20.3 CM) FLUIDIZED BED DATA SUMMARY Reaction Conditions Example2 Example 3 Production Rate 7.7 (3.5) 7.1 (3.2) (lb/hr)(kg/hr)@ SteadyState Fluidized Bulk 12-13.9 (192-223) 16-18.5 (256-296) Density(lb/ft³)(kg/m³) Seed Bed Quantity 11 (5) 22 (10) (lb)(kg) Bed Turnovers2.2 1.6 at Shutdown Theoretical wt % 0.11 0.19 seed bed at shutdownCatalyst Feed Parameters Cat Feed Rate (g/hr) 0.65 0.56 at SS, dry basisCatalyst Carriers Upstream of Mixer Isopentane (cc/hr) 200-250 na 0.5wt% TIBA in 45-90 65-100 iC₅(cc/hr) Catalyst Carriers Downstream of MixerIsopentane (cc/hr) n/a 200-250 N₂ (lb/hr)(kg/hr) 1.05 (0.5) 1.1 (0.5)Resin Properties: Melt Index 6.1 5.3 I₂ dg/min MFR (I₂₁/I₂) 17.6 18.9Density (g/ml) 0.93 0.928 Bulk Density 27.4 (439) 26 (416)(lb/ft3)(kg/m³) Average Particle 0.022 (0.06) 0.021 (0.05) Size (in)(cm)Fines <120 mesh 2.4 2.8 (wt %) Quantity (lb) 69 (31.3) 51 (23.1) Net(kg) Zr Residue 0.66 0.55 (ppmw by ICP) Al Residue 33 35 (ppmw by ICP)Si Residue 75 78 (ppmw by ICP)

Example 4 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor

[0430] Polymerization performance of in-line supported bis(n-propylcyclopentadienyl) zirconium dichloride (P-MCN) was evaluated in a 14inch (35.6 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration used for in-line activation of P-MCN with SMAO is shown inFIG. 4. Catalyst solution, fed at 10 cc/hr, was contacted with 1.0 pphisopentane carrier and 10 cc/hr of 15 wt % SMAO (as produced inExample 1) in Kaydol mineral oil upstream of the 100 ml agitated mixer.Following the mixer, catalyst was injected using a standard ⅛ inch (0.3cm) injection tube with 2.0 pph N₂ blowback.

[0431] The catalyst system was evaluated at LLDPE conditions, 85° C.,350 psig (2.4 MPa) total pressure, 200 psi (1.4 MPa) ethylene, 0.0185hexene-1 comonomer to ethylene mole ratio (C₆/C₂). A concentration of200 ppm hydrogen was maintained in the reactor. The superficial gasvelocity (SGV) was maintained at 2.0 ft/s (0.6 m/s) and the steady statebed weight at 110 lbs (50 kg). The reactor production rate was at 31pph.

[0432] The catalyst feed configuration used for in-line activation ofP-MCN with SMAO activator is shown in FIG. 4. Following the mixer,catalyst was injected using a standard ⅛ inch (0.3 cm) injection tubewith 2.0 pph N₂ blowback. Catalyst, fed at 10 cc/hr, was contacted with1.0 pph isopentane carrier and 10 cc/hr of 15 wt % SMAO (as produced inexample 1) in Kaydol mineral oil upstream of the 100 ml agitated mixer.

[0433] The product had a 5.89 dg/min (I2), 16.6 MFR and 0.926 g/ccdensity. The resin average particle size was 0.033 inches (0.084 cm)with 0.56 wt % fines (<120 mesh). The settled bulk density was 17.1lb/cu-ft. A residual zirconium of 0.28 ppm and aluminum of 35 ppm wasmeasured by X-ray fluorescence.

Example 5 Solution bis-indenyl Catalyst Compound Activated with SlurryComprising Supported Activator in Fluidized Gas-Phase Reactor

[0434] Polymerization performance of supported bis-indenyl zirconiumdichloride solution catalyst (bis-indenyl) was evaluated in a 14 inch(35.6 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration used for in-line activation of solution bis-indenylmetallocene catalyst compound with SMAO (from Example 1) is shown inFIG. 4. Catalyst, fed at 15 cc/hr, was contacted with 0.5 pph isopentanecarrier and 15 cc/hr of 15 wt % SMAO in Kaydol mineral oil upstream ofthe 100 ml agitated mixer. Following the mixer, catalyst was injectedusing a standard ⅛ inch (0.32 cm) injection tube with 1.5 pph isopentanecarrier and 4.0 pph N₂ blowback.

[0435] The catalyst system was evaluated at LLDPE conditions, 85° C.,350 psig (2.4 MPa) total pressure, 200 psi (1.4 MPa) ethylene, 0.016hexene-1 comonomer to ethylene ratio (C₆/C₂). A concentration of 195 ppmhydrogen was maintained in the reactor. The superficial gas velocity(SGV) was maintained at 2.0 ft/s (0.6 m/s) and the bed weight at 110 lbs(50 kg). The reactor production rate was 38 pph.

[0436] The product had a 8.4 dg/min (I2), 16.5 MFR and 0.9273 g/ccdensity. The resin average particle size was 0.0357 inches (0.091 cm)with 0.44 wt % fines (<120 mesh). The settled bulk density was 18.4lb/cu-ft. A residual zirconium of <0.10 ppm and aluminum of 27 ppm wasmeasured by X-ray fluorescence.

Example 6 Solution P-MCN Catalyst Compound Activated with SlurryComprising SMAO and Second Catalyst Compound in Fluidized Gas-PhaseReactor

[0437] Polymerization performance of a solution comprisingbis(n-propylcyclopentadienyl) zirconium dichloride catalyst compound anda slurry comprising SMAO and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ wasevaluated in a 14 inch (35.6 cm) fluidized bed pilot plant reactor. Thecatalyst feed configuration used for in-line activation of the solutionused the bis(n-propylcyclopentadienyl) zirconium dichloride at 0.5weight %, and a slurry comprising 17.3 weight % SMAO (from Example 1) inKaydol. (The SMAO contained 4.5 mmol Al per gram of solid). The[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ was added to the slurry off-line tomake a 150:1 molar ratio of Al:Zr. The remaining portion of the slurrywas Kaydol mineral oil. Catalyst, fed at 4 cc/hr, was contacted with 75cc/hr of the SMAO/[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ mixture in Kaydolmineral oil upstream of the series of two ten inch (25.4 cm) long ¼ inch(0.64 cm) diameter Kinecs static mixers (by Chemineer). The contact timebetween the solution and the slurry was approximately 5 minutes.Following the mixer, catalyst was injected using a standard ⅛ inch (0.32cm) injection tube with 3 pph isopentane carrier and 5 pph N₂ carrier.

[0438] The catalyst system was evaluated at the following conditions,105° C., 350 psig (2.4 MPa) total pressure, 220 psi (1.5 MPa) ethylene,and 0.0035 hexene-1 to ethylene molar ratio. A concentration of 1800 ppmhydrogen was maintained in the reactor. The superficial gas velocity(SGV) was maintained at 2.0 ft/s (0.6 m/s) and the bed weight at 75 lbs(34 kg). The reactor production rate was 21 pph.

[0439] The product had a 0.051 dg/min (I₂), 7.74 dg/min flow index, 151MFR and 0.9502 g/cc density. The resin average particle size was 0.016inches (0.04 cm) with 1.25 wt % fines (<120 mesh). The settled bulkdensity was 23.9 lb/cu-ft. A residual zirconium of <3.25 ppm andaluminum of 109 ppm was measured by X-ray fluorescence.

[0440] The data of examples 4, 5 and 6 are summarized in Table 2. TABLE2 14 INCH (35.6 CM) FLUIDIZED BED DATA SUMMARY Example 4 Example 5Example 6 Fluidized Bulk 11.0 (176) 13.0 (208) 15.4 (247) Density(lb/ft³)(kg/m³) Bed Turnovers 10.3 8.7 12 at shutdown Resin PropertiesMelt Index 5.89 8.4 0.051 (I₂ (dg/min) Flow Index 97.65 138.7 7.74(I₂₁)(dg/min) MFR (I₂₁/I₂) 16.6 16.5 151 Density (g/cc) 0.926 0.92730.9502 Bulk Density 17.1 (274) 18.4 (295) 23.9 (383) (lb/ft³)(kg/m³)Average Particle 0.033 (0.08) 0.0357 (0.090) 0.016 (0.04) Size (in)(cm)Fines < 120 0.56 0.44 1.25 mesh (wt %) Zr residue 0.28 <0.10 3.25 (ppmby X-ray) Al residue 34.7 27 109 (ppm by X-ray)

Example 7

[0441] Several product samples made from polymerization with a slurrycomprising SMAO and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, and solutionbis(n-propyl cyclopentadienyl) zirconium dichloride (P-MCN) catalystwere evaluated for film applications. This bimodal HMW HDPE granularpolymer was compounded on a 2.5 inch, 24:1 L/D single screw, equippedwith double mixing head, at 210° C., after tumble mixed with astabilizer package comprising 1,000 ppm of Irganox 1076, 1,500 ppm ofIrgafos 168, and 1,500 ppm of Calcium Stearate. Two pelleted samplesshowed 8.4 and 9.9 FI, respectively, and 155 and 140 MFR. The densitywas 0.9524 and 0.9490, respectively. The pelleted polymer was filmextruded on an Alpine film line equipped with a 50mm, 18:1 L/D singlescrew, a 100 mm die with 1 mm die gap. The die temperature was set at210° C. The output was maintained at about 100 lb/hr, the blow-up ratioof the bubble was set at 4.0, and the frost line height was 36 inches.As shown in the table below, the bimodal polymer exhibited excellentbubble stability and film extrusion characteristics. The film dartimpact strength was over 200 g and over 300 g, respectively for 1.0 miland 0.5 mil gauge. The film samples also exhibited excellent tensilestrength and modulus. Sample No. Escorene HD 7755 A B Rxn Temp (° C.)105 105 Rx pressure 350 350 C2 PP 220 220 H2/C2 (molar) 0.003 0.003 H2ppm 1800 1800 Comonomer C6 C6 Comonomer/C2 (molar) 0.004 0.0044 MI(I2)0.068 0.055 0.071 MI(I5) 0.341 FI(I21) 10 8.37 9.93 MFR (I21/I2) 146.6155 140 Density (g/cc) 0.9518 0.9524 0.9490 Ouput Rate (lb/hr) 100 101104 Head pressure (psi) 7,230 7,350 7,600 Motor Load (amp) 58 58.5 59.8BUR 4 4 4 FLH (inch) 36 36 36 Melt fracture no no no no no no FAR 40 4040 40 40 40 Bubble Stability Good fair Good Good Good Good Take-up speed(fpm) 92 182 92 184 92 184 Film gauge (mil) 1 0.5 1 0.5 1 0.5 DartImpact strength (g) 250 330 200 340 230 340 Tensile strength (psi) MD10,000 11,000 8,500 11,820 8,600 12,800 TD 7,500 7,500 6,300 8,44010,000 8,900 Elongation (%) MD 490 380 400 325 530 300 TD 570 390 630370 430 380 Elmendorf Tear (g/mil) MD 22 12 22 11 21 12 TD 186 36 360 42180 26 Modulus (psi) MD 130,400 129,400 116,000 167,200 111,000 114,000TD 160,200 163,000 146,900 164,000 127,000 136,000

[0442] ESCORENE HD7755 is a polyethylene polymer available fromExxonMobil Chemical Company in Mt. Belvue, Tex., having an I₂₁ of 7.5,and MIR of 125, an Mw of 180,000, a density of 0.95 g/cc, produced usinga dual reactor system.

[0443] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention. It is also contemplated that thecombination of the slurry and the solution immobilization technique ofthe invention can be used to essentially form, for example, ametallocene catalyst compound that is combined with an activator and fedto a polymerization reactor.

[0444] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

We claim:
 1. A process to produce a multimodal polyolefin in a singlereactor comprising: a) continuously combining a catalyst componentslurry with a catalyst component solution to form a catalystcomposition; b) combining the catalyst composition with one or moreolefin(s) in a polymerization reactor to form a multimodal polyolefin;c) measuring a sample of the multimodal polyolefin to obtain an initialmultimodal polyolefin property; d) changing the amount of catalystcomponent solution combined in (a) relative to the amount of catalystcomponent slurry to obtain a second product property; and e) isolatingthe multimodal polyolefin product; wherein the catalyst component slurrycomprises one or more catalyst compounds, one or more activators and oneor more support materials; and the catalyst component solution comprisesone or more catalyst compounds, wherein the catalyst compounds may bethe same or different.
 2. The process of claim 1, wherein the catalystcomponent slurry comprises a first catalyst compound and the catalystcomponent solution comprises a second catalyst compound.
 3. The processof claim 2, wherein the first catalyst compound is a Group 15 containingmetal compound and where in the second catalyst compound is a bulkyligand metallocene compound.
 4. The process of claim 2, wherein themolar ratio of the first catalyst compound to the second catalystcompound in the catalyst composition is between about 500:1 to about1:500.
 5. The process of claim 1, wherein the polyolefin property isselected from the group consisting of flow index (I₂₁), melt index (I₂),density, MWD (M_(w)/M_(n)), comonomer content, and combinations thereof.6. The process of claim 1, wherein polyolefin property is flow index(I₂₁).
 7. The process of claim 1, wherein the reactor is a gas phasefluidized bed reactor.
 8. The process of claim 7, wherein the reactortemperature is from 60 to 115° C.
 9. The process of claim 1, wherein thecatalyst composition is passed through an injection tube extending intothe reactor a distance of 0.25 cm to 3.1 m.
 10. The process of claim 1,wherein the catalyst composition is passed through an injection tubeextending into the reactor a distance of 5 cm to 1.5 m.
 11. The processof claim 9 or 10, wherein a carrier stream comprising an alkane iscontacted with the catalyst composition prior to passing through theinjection tube.
 12. The process of claim 11, wherein the carrier streamfurther comprises a carrier gas.
 13. The process of claim 1, wherein thecatalyst component slurry comprises mineral oil.
 14. The process ofclaim 1, wherein the polyolefin product is a multimodal or bimodalpolyethylene comprising a high molecular weight fraction and a lowmolecular weigh fraction; the polymer product having a density of from0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to
 50. 15. The processof claim 1, wherein the polyolefin product is a multimodal or bimodalpolyethylene comprising a high molecular weight fraction and a lowmolecular weigh fraction; and wherein the weight percent ratio is higherthan 10 and less than
 30. 16. The process of claim 1, wherein thepolyolefin product is a multimodal or bimodal polyethylene comprising ahigh molecular weight fraction and a low molecular weigh fraction; andwherein the weight percent ratio is higher than 15 and less than
 25. 17.The process of claim 1, wherein the multimodal polyolefin is separatedinto fractions according to the following table: Fraction Sieve sizeFraction Collected Name 10 mesh >2000 μm Fraction 1 18 mesh 2000-1000 μmFraction 2 35 mesh <1000-500 μm Fraction 3 60 mesh <500-250 μm Fraction4 120 mesh <250-125 μm Fraction 5 200 mesh/Pan <125 μm Fraction 6

and the melt indices of Fractions 3, 4 and 5 do not vary by more than30% relative to each other.
 18. The process of claim 3, wherein theGroup 15 containing catalyst compound is represented by the formulae:

wherein M is a Group 4, 5, or 6 metal; each X is independently a leavinggroup; y is 0 or 1, wherein when y is 0, group L′ is absent; n is theoxidation state of M; m is the formal charge of the ligand representedby YZL and YZL′; L, L′, Y and Z are each a Group 15 element; R¹ and R²are independently a C₁ to C₂₀ hydrocarbon group, a heteroatom containinggroup having up to twenty carbon atoms, silicon, germanium, tin, lead,halogen or phosphorus; R³ is absent or a hydrocarbon group, hydrogen, ahalogen, a heteroatom containing group; R⁴ and R⁵ are independently analkyl group, an aryl group, substituted aryl group, a cyclic alkylgroup, a substituted cyclic alkyl group, a cyclic arylalkyl group, asubstituted cyclic arylalkyl group or multiple ring system; R⁶ and R⁷are independently absent, or hydrogen, an alkyl group, halogen,heteroatom or a hydrocarbyl group; and R* is absent, or is hydrogen, aGroup 14 atom containing group, a halogen, or a heteroatom containinggroup.
 19. The process of claim 3, wherein the bulky ligand metallocenecatalyst compound is represented by the following formulae:L^(A)L^(B)MQ_(n) or L^(A)AL^(B)MQ_(n) wherein M is a Group 4, 5 or 6transition metal; bulky ligands L^(A) and L^(B) are each bound to M andare unsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted or heteroatomcontaining cyclopentadienyl-type ligands; Q is a monoanionic labileligand; wherein each Q is bound to M; A is a divalent bridging moietybound to each of L^(A) and L^(B); and n is 0, 1 or 2
 20. The process ofclaim 1, wherein the support material is fumed silica.
 21. A film, pipeor blow molded product comprising the multimodal polyolefin of claim 1.